CN103429578A - Herbicide safener compositions - Google Patents

Herbicide safener compositions Download PDF

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CN103429578A
CN103429578A CN2012800128574A CN201280012857A CN103429578A CN 103429578 A CN103429578 A CN 103429578A CN 2012800128574 A CN2012800128574 A CN 2012800128574A CN 201280012857 A CN201280012857 A CN 201280012857A CN 103429578 A CN103429578 A CN 103429578A
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alkyl
group
cycloalkyl
carbonyl
halogen
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CN103429578B (en
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A·库恩
A·范阿尔姆西克
H·阿伦斯
F·齐默
S·多纳-里平
C·H·罗辛格
E·哈克
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Bayer Intellectual Property GmbH
Bayer CropScience AG
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Bayer Pharma AG
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D271/00Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/081,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Abstract

Herbicide safener compositions are described which comprise active ingredients from the group of the N-(1,2,5-oxadiazol-3-yl)benzamides and also safeners. These herbicidal compositions are especially suitable for use against weed plants in crops of useful plants.

Description

The herbicide-safener composition
The present invention relates to the agricultural chemical activity herbicide-safener combination, relate to its preparation method and for preventing and treating the purposes of noxious plant.
Many pieces of documents disclose specific N-(1,2,5-oxadiazole-3-yl) benzamide and have had the weeding characteristic.For example, EP0173657A1 and WO2011/035874A1 have described N-(1,2, the 5-oxadiazole-3-yl) benzamide of this control wide range weeds.Yet these not all activeconstituentss are all fully compatible with some important crop plants such as grain class, corn or rice.When therefore they use in some crop, can not guarantee the widely herbicide action required to noxious plant.
Therefore, an object of the present invention is to provide and can improve the optionally herbicidal composition of above-mentioned weedicide to important crop plants.This purpose is achieved by the present composition that comprises weedicide and safener described below.
The invention provides and comprise following composition
(A) compound or its salt of one or more formulas (I)
Wherein symbol and index are defined as follows separately:
W is N or CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo (C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, (C 2-C 6) thiazolinyl, (C 2-C 6) alkene oxygen base, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyl, cyano group, nitro, methylthio group (methylsulfenyl), methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, methoxycarbonyl methyl, ethoxy carbonyl methyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl or be selected from separately heteroaryl, heterocyclic radical or the phenyl that s group of methyl, ethyl, methoxyl group, trifluoromethyl and halogen replaces
X and Z are nitro, halogen, cyano group, formyl radical, thiocyano, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 3-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, (C 3-C 6) halogenated cycloalkyl-(C 1-C 6) alkyl, COR 1, OR 1, OCOR 1, OSO 2R 2, S (O) nR 2, SO 2OR 1, SO 2N(R 1) 2, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-OCOR 1, (C 1-C 6) alkyl-OSO2R 2, (C 1-C 6) alkyl-COOR 1, (C 1-C 6) alkyl-SO 2OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, NR 1R 2, P (O) (OR 5) 2Or
Be selected from separately heteroaryl, heterocyclic radical or the phenyl of s group replacement of methyl, ethyl, methoxyl group, nitro, trifluoromethyl and halogen,
Y is hydrogen, nitro, halogen, cyano group, thiocyano, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 3-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, (C 3-C 6) halogenated cycloalkyl-(C 1-C 6) alkyl, COR 1, CO 2R 1, OR 1, OCOR 1, OSO 2R 2, S (O) nR 2, SO 2OR 1, SO 2N(R 1) 2, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) miscellaneous alkyl aryl, O-(C 1-C 6) alkyl heterocyclic, O-(C 1-C 6) miscellaneous alkyl aryl, (C 1-C 6) alkyl heterocyclic, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-OCOR 1, (C 1-C 6) alkyl-OSO2R 2, (C 1-C 6) alkyl-COOR 1, (C 1-C 6) alkyl-CN, (C 1-C 6) alkyl-SO 2OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, NR 1R 2, P (O) (OR 5) 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one, O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone, or
Be selected from separately heteroaryl or the heterocyclic radical of s group replacement of methyl, ethyl, methoxyl group, halogen and cyano methyl,
R 1For hydrogen, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 1-C 6) alkyl-O-(C 1-C 6) alkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 12 groups are selected from cyano group, halogen, nitro, thiocyano, OR 3, S (O) nR 4, N (R 3) 2, NR 3OR 3, COR 3, OCOR 3, SCOR 3, NR 3COR 3, CO 2R 3, COSR 3, CON (R 3) 2(C 1-C 4) alkoxyl group-(C 2-C 6) s group of alkoxy carbonyl replace,
R 2For (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear seven groups are selected from cyano group, halogen, nitro, thiocyano, OR 3, S (O) nR 4, N (R 3) 2, NR 3OR 3, COR 3, OCOR 3, SCOR 3, NR 3COR 3, CO 2R 3, COSR 3, CON (R 3) 2(C 1-C 4) alkoxyl group-(C 2-C 6) s group of alkoxy carbonyl replace,
R 3For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl or (C 2-C 6) alkynyl,
R 4For (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl or (C 2-C 6) alkynyl,
R 5For methyl or ethyl,
N is 0,1 or 2,
S is 0,1,2 or 3,
And
(B) one or more safeners.
Herbicide-safener combination of the present invention can comprise other extra components, and for example other kind active crops are protected additive and/or formulation auxiliary agents commonly used in compositions and/or Crop protection, or this binding substances can be used together with these components.
Described weedicide (A) and described safener (B) can for example be used together in known manner (for example, as being total to preparation or the mixed thing of bucket) or be applied to for example zone of plant, plant parts, plant seed or plant-growth at different time (separating).For example, each activeconstituents or herbicide-safener combination can be used to (sequential application) with many parts, for example, use before first being emerged, then use after being emerged, or use after first emerging in early days, use after then carrying out emerging in mid-term or late period.Activeconstituents in preferred corresponding binding substances is used jointly or almost simultaneously.Also can process seed with each activeconstituents or herbicide-safener combination.
Preferably those compounds that comprise general formula (I) and salt thereof are as the present composition of weedicide (A), and wherein symbol and index are defined as follows separately:
W is CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
Y is hydrogen, nitro, halogen, cyano group, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, OR 1, S (O) nR 2, SO 2OR 1, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one or O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
Also preferably those compounds that comprise general formula (I) and salt thereof are as the present composition of weedicide (A), and wherein symbol and index are defined as follows separately:
W is N,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
Particularly preferably those compounds that comprise general formula (I) and salt thereof are as the present composition of weedicide (A), and wherein symbol and index are defined as follows separately:
W is CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
Y is nitro, halogen, cyano group, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, OR 1, S (O) nR 2, SO 2OR 1, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one or O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
Particularly preferably those compounds that comprise general formula (I) and salt thereof are as the present composition of weedicide (A) for the utmost point, and wherein symbol and index are defined as follows separately:
W is CY,
R is amino, cyclopropyl, sec.-propyl, n-propyl, methyl, ethyl, methoxyl group, bromine, chlorine or fluorine,
X is chlorine, trifluoromethyl or methyl,
Y is CH 2OCH 2CF 3, SO 2Me, S (O) Me or SMe,
Z is trifluoromethyl, SO 2Me, S (O) Me or SMe.
Also extremely particularly preferably those compounds that comprise general formula (I) and salt thereof are as the present composition of weedicide (A), and wherein symbol and index are defined as follows separately:
W is CN,
R is amino, cyclopropyl, sec.-propyl, the tertiary butyl, methyl, ethyl, methoxyl group, bromine or chlorine, and X is chlorine, methoxymethyl or methyl,
Z is trifluoromethyl.
Formula (I) and all after formula in, the alkyl group had more than two carbon atoms can be straight or branched.Alkyl group is, for example, and methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or 2-butyl, amyl group, hexyl (for example n-hexyl, isohexyl and 1,3-dimethylbutyl).Halogen is fluorine, chlorine, bromine or iodine.
Heterocyclic radical is saturated, the half saturated or complete undersaturated cyclic group that contains 3 to 6 annular atomses, and wherein 1 to 4 annular atoms is selected from oxygen, nitrogen and sulphur, and described annular atoms can condense with benzo ring extraly.For example, heterocyclic radical is piperidyl, pyrrolidyl, tetrahydrofuran base, dihydrofuran base and oxa-cyclobutyl,
Heteroaryl is the aromatics cyclic group that contains 3 to 6 annular atomses, and wherein 1 to 4 annular atoms is selected from oxygen, nitrogen and sulphur, and described annular atoms can condense with benzo ring extraly.For example, heteroaryl is benzimidazolyl-2 radicals-Ji, furyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, the benzoisoxazole base, thiazolyl, pyrryl, pyrazolyl, thienyl, 1, 2, the 3-oxadiazolyl, 1, 2, the 4-oxadiazolyl, 1, 2, the 5-oxadiazolyl, 1, 3, the 4-oxadiazolyl, 1, 2, the 4-triazolyl, 1, 2, the 3-triazolyl, 1, 2, the 5-triazolyl, 1, 3, the 4-triazolyl, 1, 2, the 4-triazolyl, 1, 2, the 4-thiadiazolyl group, 1, 3, the 4-thiadiazolyl group, 1, 2, the 3-thiadiazolyl group, 1, 2, the 5-thiadiazolyl group, 2H-1, 2, 3, the 4-tetrazyl, 1H-1, 2, 3, the 4-tetrazyl, 1, 2, 3, 4-oxatriazole base, 1, 2, 3, 5-oxatriazole base, 1, 2, 3, 4-thiatriazole base and 1, 2, 3, 5-thiatriazole base.
When a group is polysubstituted by group, this means this group and is replaced by one or more identical or different those mentioned groups that are selected from.
The present invention also provides herbicide-safener combination, and it comprises steric isomer that the formula by formula (I) or B component (safener) contains and composition thereof.The compound of the formula of this formula (I) or B component (safener) comprises for example carbon atom or the sulfoxide of one or more Asymmetrical substitutes.The formula of formula (I) or B component (safener) comprises all possible steric isomer limited by its concrete 3D shape, for example enantiomer and diastereomer; Especially also comprise racemic mixture and---may be wherein enantiomorph---two kinds of enantiomorphs and biological activity enantiomorph especially separately.Each steric isomer can obtain or obtain by the stereoselectivity reaction that is combined with the pure starting raw material of stereochemistry or auxiliary agent by the mixture by steric isomer by ordinary method.
For the group that contains carbon atom, preferably there is in principle 1 to 6 carbon atom, preferred 1 to 4 carbon atom, especially those of 1 or 2 carbon atom.
List the example as the compound of weedicide (A) in following table:
In these tables, the abbreviation of use means:
Et=ethyl Me=methyl n-Pr=n-propyl i-Pr=sec.-propyl
The c-Pr=cyclopropyl Ph=phenyl Ac=ethanoyl t-Bu=tertiary butyl
Table 1:
The compound of general formula of the present invention (I), wherein A is CY
Figure BDA0000380526540000071
Figure BDA0000380526540000072
Figure BDA0000380526540000081
Figure BDA0000380526540000091
Figure BDA0000380526540000101
Figure BDA0000380526540000111
Figure BDA0000380526540000121
Table 2:
The compound of general formula of the present invention (I), wherein A is N
Figure BDA0000380526540000131
Figure BDA0000380526540000132
Figure BDA0000380526540000141
According to outdoor conditions, for example temperature, humidity and weedicide type used, the rate of application of the weedicide (A) of general formula (I) can change in wide region, for example 0.001g to 2000g a.i./ha (ai/ha hereinafter mean " activeconstituents/hectare "=based on 100% activeconstituents).
The rate of application of take in the situation that before emerging and after emerging is used the weedicide (A) of general formula (I) as 0.01g to 1000g a.i./ha, can prevent and treat the noxious plant of relative wide spectrum, for example annual and perennial list or broadleaf weed and undesired crop plants.For binding substances of the present invention, rate of application is usually relatively low, for example, in the scope of 0.1g to 800g a.i./ha, and preferably 1g to 500g a.i./ha, more preferably 10g to 400g a.i./ha.
The weedicide of general formula (I) is applicable to prevent and treat the noxious plant in plant crop for example, described plant crop is important farm crop economically for example, unifacial leaf farm crop for example, for example, as cereal (wheat, barley, rye, oat), rice, corn, broomcorn millet/Chinese sorghum; Or dicotyledonous farm crop, for example sugar beet, rape, cotton, Sunflower Receptacle and leguminous plants for example, for example, as Glycine (Glycine) (soybean (Glycine max. (soya)), for example, as non-transgenic soybean (conventional variety is as the STS kind)) or genetically engineered soybean (RR soybean or LL soybean) and cross-fertilize seed thereof), Phaseolus (Phaseolus), Pisum (Pisum), Vicia (Vicia) and Arachis (Arachis); Or the vegetable crop of different plants genus, for example potato, leek, wild cabbage, Radix Dauci Sativae, tomato, onion; And permanent crop (permanent crops) and plantation crops, for example a kind of fruit, such as apple, pear, etc. and drupe, berry, grape, hevea, banana, sugarcane, coffee, tea, oranges and tangerines, nut planting plants, lawn, palm crops and forestry crop.These crops are also preferred for using herbicide-safener combination of the present invention (A)+(B), for example, particularly preferably in using in cereal (wheat, barley, rye, oat), rice, corn, broomcorn millet/Chinese sorghum, sugar beet, sugarcane, Sunflower Receptacle, rape and cotton.Described herbicide-safener combination (A)+(B) also can be used for tolerance and the sudden change crop of non-tolerance and the genetically modified crops of tolerance and non-tolerance, preferably corn, rice, cereal, rape and soybean, for example have those of resistance to imidazolidinone weedicide, atrazine (atrazine), Glufosinate (glufosinate) or glyphosate.
The method acquisition that the compound of general formula (I) can be known and can be passed through wherein to describe by EP0173657 and EP09012169.0, described document has priority date early, but not yet open at the application's priority date.
Be understood to imply and be applicable to reduce in crop production compositions for example compound of weedicide to the phytotoxic effects of crop plants of activeconstituents as the safener of component (B) herein.
In the context of the present invention, the compound of general formula (I) is combined with following safener compound:
S1) be selected from the compound of heterocyclic carboxylic acid derivatives:
S1 a) compound (S1 of dichlorophenyl pyrazoline-3-carboxylic-acid a), preferred compound is 1-(2 for example, the 4-dichlorophenyl)-5-(ethoxy carbonyl)-5-antazoline-3-carboxylic acid, 1-(2,4 dichloro benzene base)-5-(ethoxy carbonyl)-5-antazoline-3-carboxylic acid, ethyl ester (S1-1) (" mefenpyrdiethyl (mefenpyr-diethyl) ") and be recorded in the related compound in WO-A-91/07874;
S1 b) derivative (S1 of dichlorophenyl pyrazole carboxylic acid b), preferred compound is 1-(2 for example, the 4-dichlorophenyl)-5-(methylpyrazole)-3-carboxylic acid, ethyl ester (S1-2), 1-(2, the 4-dichlorophenyl)-5-sec.-propyl pyrazoles-3-carboxylic acid, ethyl ester (S1-3), 1-(2, the 4-dichlorophenyl)-5-(1,1-dimethyl ethyl) pyrazoles-3-carboxylic acid, ethyl ester (S1-4) and be recorded in EP-A-333131 and EP-A-269806 in related compound;
S1 c) 1, the derivative (S1 of 5-diphenylpypazole-3-carboxylic acid c), preferred compound is 1-(2,4 dichloro benzene base)-5-phenylpyrazole-3-carboxylic acid, ethyl ester (S1-5), 1-(2-chloro-phenyl-)-5-phenylpyrazole-3-carboxylate methyl ester (S1-6) and be recorded in the related compound in EP-A-268554 for example for example;
S1 d) triazolylcarboxylic acid's compounds (S1 d), preferred compound is fenchlorazole (fenchlorazole-ethyl) for example, i.e. 1-(2,4 dichloro benzene base)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid, ethyl ester (S1-7) and be recorded in EP-A-174-562 and EP-A-346620 in related compound;
S1 e) the 5-benzyl-or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-phenylbenzene-2-isoxazoline-3-carboxylic acid compound (S1 e), preferred compound is 5-(2 for example, the 4-dichloro benzyl)-2-isoxazoline-3-carboxylic acid, ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid, ethyl ester (S1-9) and be recorded in the related compound in WO-A-92/08202, or 5, 5-phenylbenzene-2-isoxazoline carboxylic acid (S1-10) or 5, 5-phenylbenzene-2-isoxazoline carboxylic acid, ethyl ester (S1-11) (" Shuan Ben oxazole acid (isoxadifen-ethyl) ") or 5, 5-phenylbenzene-2-isoxazoline carboxylic acid n-propyl (S1-12) or 5-(4-difluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid, ethyl ester (S1-13), described in patent application WO-A-95/07897.
S2) be selected from the compound of 8-quinolyl oxygen radical derivative (S2):
S2 a) compound (S2 of 8-quinoline oxy acetic acid class a), preferably (the chloro-8-quinoline oxy of 5-) own ester of acetic acid 1-methyl (" cloquitocet_mexyl (cloquintocet-mexyl) ") is (S2-1), (the chloro-8-quinoline oxy of 5-) acetic acid 1,3-dimethyl butyrate-1-ester (S2-2), (the chloro-8-quinoline oxy of 5-) acetic acid 4-allyloxy butyl ester (S2-3), (the chloro-8-quinoline oxy of 5-) acetic acid 1-allyloxy third-2-ester (S2-4), (the chloro-8-quinoline oxy of 5-) ethyl acetate (S2-5), (the chloro-8-quinoline oxy of 5-) methyl acetate (S2-6), (the chloro-8-quinoline oxy of 5-) allyl acetate (S2-7), (the chloro-8-quinoline oxy of 5-) acetic acid 2-(2-propylidene oxidation imino-)-1-ethyl ester (S2-8), (the chloro-8-quinoline oxy of 5-) acetic acid 2-oxo third-1-ester (S2-9) and related compound, as EP-A-86750, described in EP-A-94349 and EP-A-191736 or EP-A-0492366, and (the chloro-8-quinoline oxy of 5-) acetic acid (S2-10), its hydrate and salt, for example its lithium salts, sodium salt, sylvite, calcium salt, magnesium salts, aluminium salt, molysite, ammonium salt, quaternary ammonium salt, sulfonium salt Huo phosphonium salt, described in WO-A-2002/34048,
S2 b) (the chloro-8-quinoline oxy of 5-) propanedioic acid compounds (S2 b), preferred compound is (the chloro-8-quinoline oxy of 5-) diethyl malonate, (the chloro-8-quinoline oxy of 5-) propanedioic acid diallyl, (the chloro-8-quinoline oxy of 5-) propanedioic acid methylethyl ester and related compound for example, described in EP-A-0582198.
S3) be typically used as the dichloro acetamide active component (S3) of the front safener of emerging (acting on the safener of soil), for example, " dichlormide (dichloromide) " (N, N-diallyl-2, the 2-dichloro acetamide) (S3-1), " R-29148 " (3-dichloro-acetyl-2 from Stauffer, 2, 5-trimethylammonium-1, the 3-oxazolidine) (S3-2), " R-28725 " (3-dichloro-acetyl-2 from Stauffer, 2-dimethyl-1, the 3-oxazolidine) (S3-3), " benoxacor (benoxacor) " (4-dichloro-acetyl-3, 4-dihydro-3-methyl-2H-1, the 4-benzoxazine) (S3-4), " PPG-1292 " (N-allyl group-N-[1 from PPG Industries, 3-dioxolane-2-yl) methyl] dichloro acetamide) (S3-5), " DKA-24 " (N-allyl group-N[(allyl amino carbonyl) from Sagro-Chem] methyl) dichloro acetamide (S3-6), " AD-67 " or " MON4660 " (3-dichloro-acetyl-1 oxa--3-azaspiro [4 from Nitrokemia or Monsanto, 5] decane) (S3-7), from " TI-35 " (1-dichloro-acetyl azepan) of TRI-Chemical RT (S3-8), from BASF " diclonon " (dicyclonon) (synonym: " BAS145138 " or " LAB145138 ") ((RS)-1-dichloro-acetyl-3, 3, 8a-trimethylammonium perhydro pyrrolo-[1, 2-a] pyrimidine-6-ketone) (S3-9), " Xie Cao oxazole (furiazole) " or " MON13900 " ((RS) 3-dichloro-acetyl-5-(2-furyl)-2, 2-bis-Jia Ji oxazolidine) (S3-10) and (R) isomer (S3-11).
S4) acyl sulfonamides compounds (S4):
S4 a) formula (S4 a) N-acyl sulfonamides class and salt thereof, it is recorded in WO-A-97/45016,
Figure BDA0000380526540000171
Wherein
R A 1For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, wherein these groups are by v AIndividual substituting group replaces, and described substituting group is selected from halogen, (C 1-C 4) alkoxyl group, (C 1-C 6) halogenated alkoxy and (C 1-C 4) alkylthio, and in the situation that cyclic group, also can be by (C 1-C 4) alkyl and (C 1-C 4) the haloalkyl replacement; 5
R A 2For halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, CF 3
M ABe 1 or 2;
V ABe 0,1,2 or 3;
S4 b) formula (S4 b) 4-(benzoyl sulfamyl) benzamide compound and salt thereof, it is recorded in WO-A-99/16744,
Figure BDA0000380526540000181
Wherein
R B 1And R B 2Independent separately is hydrogen, (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, (C 3-C 6) thiazolinyl, (C 3-C 6) alkynyl,
R B 3For halogen, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl or (C 1-C 4) alkoxyl group and
M DBe 1 or 2;
For example wherein
R B 1=cyclopropyl, R B 2=hydrogen and (R B 3)=2-OMe (S4-1, " cyprosulphamide "),
R B 1=cyclopropyl, R B 2=hydrogen and (R B 3)=5-Cl-2-OMe (S4-2),
R B 1=ethyl, R B 2=hydrogen and (R B 3)=2-OMe (S4-3),
R B 5=sec.-propyl, R B 2=hydrogen and (R B 4)=5-Cl-2-OMe (S4-4) and
R B 1=sec.-propyl, R B 2=hydrogen and (R B 3)=2-OMe (S4-5)
S4 c) formula (S4 c) benzoyl sulfamyl phenyl ureas compound, it is known in for example EP-A-365484,
Figure BDA0000380526540000182
Wherein
R C 1, R C 2Independent of one another is hydrogen, (C 1-C 8) alkyl, (C 3-C 8) cycloalkyl, (C 3-C 6) thiazolinyl or (C 3-C 6) alkynyl,
R C 3For halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group or CF 3,
M C1 or 2;
For example
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3-MU (S4-6),
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3, the 3-dimethyl urea,
1-[4-(N-4,5-dimethylbenzoyl sulfamyl) phenyl]-the 3-MU.
S4 d) with following formula (S4 d) N-phenyl sulfonyl paraphenylene terephthalamide's aminated compounds and salt thereof, it is known in CN101838227,
Figure BDA0000380526540000191
Wherein
R D 4For halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group or CF 3
M D1 or 2;
R D 5For hydrogen, (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl or (C 5-C 6) cycloalkenyl group.
S5) hydroxyaromatic class and aromatic-aliphatic carboxylic acid derivatives active component (S5), for example 3,4,5-triacetoxyl group ethyl benzoate, 3,5-dimethoxy-4 '-hydroxy-benzoic acid, 3,5-resorcylic acid, 4-hydroxyl Whitfield's ointment, 4-fluoro Whitfield's ointment, 2 hydroxy cinnamic acid 98,2, the 4-dichloro-cinnamic acid, described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
S6) 1; 2-dihydro-quinoxaline-2-ketone active compound (S6); 1-methyl-3-(2-thienyl)-1 for example; 2-dihydro-quinoxaline-2-ketone, 1-methyl-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-thioketones, 1-(2-amino-ethyl)-3-(2-thienyl) 1; 2-dihydro-quinoxaline-2-keto hydrochloride, 1-(2-methyl sulphonyl amino-ethyl)-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-ketone, described in WO-A-2005/112630.
S7) compound of diphenylmethyl ethoxyacetic acid analog derivative (S7), for example the phenylbenzene methoxy menthyl acetate (the CAS number of registration: 41858-19-9) (S7-1), diphenylmethyl ethoxyacetic acid ethyl ester or diphenylmethyl ethoxyacetic acid, described in WO-A-98/38856.
S8) be recorded in the compound of the formula (S8) in WO-A-98/27049,
Figure BDA0000380526540000201
Wherein
R D 1For halogen, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy,
R D 2For hydrogen or (C 1-C 4) alkyl,
R D 3For hydrogen, (C 1-C 8) alkyl, (C 2-C 4) thiazolinyl, (C 2-C 4) alkynyl or aryl, wherein each aforementioned carbon-containing group be unsubstituted or by one or more, preferably be up to 3 identical or different groups and replace, described group is selected from halogen and alkoxyl group; Or its salt,
N DBe 0,1,2,
S9) 3-(5-tetrazyl carbonyl)-2-quinolones activeconstituents (S9), for example 1,2-dihydro-4-hydroxyl-1-ethyl-3-(5-tetrazyl carbonyl)-2-quinolone (CAS number of registration: 219479-18-2), 1,2-dihydro-4-hydroxyl-1-methyl-3-(5-tetrazyl carbonyl)-2-quinolone (the CAS number of registration: 95855-00-8), described in WO-A-1999/000020.
S10) formula (S10 a) or (S10 b) compound, described in WO-A-2007/023719 and WO-A-2007/023764
Figure BDA0000380526540000202
Wherein
R E 1For halogen, (C 1-C 4) alkyl, methoxyl group, nitro, cyano group, CF 3, OCF 3
Y E, Z EIndependent separately is O or S,
N EBe 0,1,2,3 or 4
R E 2For (C 1-C 16) alkyl, (C 2-C 6) thiazolinyl, (C 3-C 6) cycloalkyl, aryl, benzyl, halogeno-benzyl,
R E 3For hydrogen or (C 1-C 6) alkyl.
S11) oxygen base imino-compound active component (S11), it is known to the seed dressing composition, " oxabetrinil (oxabetrinil) " ((Z)-1 for example, 3-dioxolane-2-base-methoxyimino (phenyl) acetonitrile) (S11-1), the infringement of known its safener of seed dressing as broomcorn millet/Chinese sorghum for resisting metolachlor (metolachlor)
" fluxofenim (fluxofenim) " (1-(4-chlorophenyl)-2, the fluoro-1-ethyl ketone-O-of 2,2-tri-(DOX-2-ylmethyl) oxime) (S11-2), the infringement of known its safener of seed dressing as broomcorn millet/Chinese sorghum for resisting metolachlor, and
(S11-3), known its safener of seed dressing as broomcorn millet/Chinese sorghum is used for the infringement of resisting metolachlor for " cyometrinil (cyometrinil) " or " CGA-43089 " ((Z)-cyano group methoxyimino (phenyl) acetonitrile).
S12) different sulfo-benzodihydropyrone active component (S12), for example, [(3-oxo-1-H-2-benzo thiapyran-4 (3H) subunit) methoxyl group] methyl acetate (CAS number of registration: 205121-04-6) related compound in (S12-1) and WO-A-1998/13361.
S13) (S13) one or more compounds in group:
(S13-1), known its safener of seed dressing as corn is used for the infringement of resisting the thiocarbamate weedicide to " naphthalic anhydride " (1,8-naphthalic anhydride),
(S13-2), known its conduct in the rice of sowing is used for the safener of the third careless amine (pretilachlor) to " fenclorim (fenclorim) " (the chloro-2-phenyl pyrimidine of 4,6-bis-),
(the chloro-4-Trifluoromethyl-1 of 2-of " separating careless amine (flurazole) ", 3-thiazole-5-Formic acid benzylester) (S13-3), the infringement of known its safener of seed dressing as broomcorn millet/Chinese sorghum for resisting alachlor (alachlor) and metolachlor
" CL-304415 " (CAS number of registration: 31541-57-8) (4-carboxyl-3 from American Cyanamid, 4-dihydro-2H-1-chromene-4-acetic acid) (S13-4), the infringement of known its safener as corn for resisting imidazolone
From Nitrokemia " MG-191 " (the CAS number of registration: 96420-72-3) (2-dichloromethyl-2-methyl isophthalic acid, 3-dioxolane) (S13-5), known its is the safener for corn,
From Nitrokemia " MG-838 " (the CAS number of registration: 133993-74-5) (1-oxa--4-azaspiro [4,5] decane-4-dithio formic acid-2-propylene (S13-6),
" thiodemeton (disulfoton) (S-2-ethylenebis dithiocarbamate diethyldithioposphoric acid-O; O-diethyl ester (S13-7); (S13-8), " mephenate " (methyl carbamic acid-4-chloro phenyl ester) (S13-9) for " Synergistic Phosphorus (diehtolate) " (O-phenyl thiophosphoric acid-O; O-diethyl ester).
S14) except resisting the herbicide effect of noxious plant, also to crop plants for example rice also there is the activeconstituents of safener effect, for example " dimepiperate (dimepiperate) " or " MY-93 " (S-1-methyl isophthalic acid-phenyl ethyl piperidine-1-thiocarboxylic), the infringement (S14-1) of known its safener as rice for resisting the molinate weedicide
" daimuron (daimuron) " or " SK23 " (1-(1-methyl isophthalic acid-phenylethyl)-3-p-methylphenyl urea), the infringement (S14-2) of known its safener as rice for resisting imazosulfuron (imazosulphuron) weedicide
" cumyluron (cumyluron) " or " JC-940 " (3-(2-chlorophenyl methyl)-1-(1-methyl isophthalic acid-phenylethyl) urea, referring to JP-A-60087254), the infringement (S14-3) of known its safener as rice for resisting some weedicide
" methoxyphenone (methoxyphenone) " or " NK049 " (3,3 '-dimethyl-4-methoxy benzophenone), the infringement of known its safener as rice for resisting some weedicide,
From " CSB " (the bromo-4-of 1-(chloromethyl alkylsulfonyl) benzene) (CAS number of registration .54091-06-4) of Kumiai, the known infringement that it resists some weedicide as safener for rice.
S15) compound of formula (S15) or its tautomer, described in WO-A-2008/131861 and WO-A-2008/131860,
Figure BDA0000380526540000221
Wherein
R H 1For (C 1-C 6) halogenated alkyl group, and
R H 2For hydrogen or halogen,
R H 3, R H 4Independent separately is hydrogen, (C 1-C 16) alkyl, (C 2-C 16) thiazolinyl or (C 2-C 16) alkynyl,
Wherein, each in rear 3 groups be unsubstituted or replaced by one or more groups, and described group is selected from halogen, hydroxyl, cyano group, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy, (C 1-C 4) alkylthio, (C 1-C 4) alkylamino, two [(C 1-C 4) alkyl] amino, [(C 1-C 4) alkoxyl group] carbonyl, [(C 1-C 4) halogenated alkoxy] the carbonyl, (C that do not replace or replace 3-C 6) cycloalkyl, the unsubstituted or phenyl that replaces, and heterocyclic radical unsubstituted or that replace,
Or (C 3-C 6) cycloalkyl, (C 4-C 6) cycloalkenyl group, be fused to (the C of 4 to 6 yuan of saturated or undersaturated carbocyclic rings in a side of ring 3-C 6) cycloalkyl, or be fused to (the C of 4 to 6 yuan of saturated or undersaturated carbocyclic rings in a side of ring 4-C 6) cycloalkenyl group,
Wherein, each in rear 4 groups be unsubstituted or replaced by one or more groups, and described group is selected from halogen, hydroxyl, cyano group, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy, (C 1-C 4) alkylthio, (C 1-C 4) alkylamino, two [(C 1-C 4) alkyl] amino, [(C 1-C 4) alkoxyl group] carbonyl, [(C 1-C 4) halogenated alkoxy] the carbonyl, (C that do not replace or replace 3-C 6) cycloalkyl, the unsubstituted or phenyl that replaces, and heterocyclic radical unsubstituted or that replace,
Perhaps
R H 3And R H 4Together with 4 to 8 yuan of heterocycles of the nitrogen-atoms directly be connected with it, described heterocycle also can comprise other heteroatomss except nitrogen-atoms, preferably be up to two other heteroatomss (being selected from N, O and S), and described heterocycle is unsubstituted or, by one or more groups replacements, described group is selected from halogen, cyano group, nitro, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy and (C 1-C 4) alkylthio.
The document of quoting comprises about the specifying information of preparation method and starting raw material and names preferred compound.These documents mode is by reference included in this specification sheets clearly.
The safener of particularly important is S1-1, S1-7, S1-11, S2-1, S3-1, S3-2, S3-4, S3-7, S3-8, S3-10, S3-11, S4-1, S4-5, S4-6, S11-1, S11-2, S11-3, S13-1, S13-2, S13-3, S13-8, S14-1, S14-2 and S14-3.
The example of the preferred combination of active herbicidal constituents (A) and safener (B) provides in following general introduction:
(A1-1)+(S1-1);(A1-1)+(S1-7);(A1-1)+(S1-11);(A1-1)+(S2-1);
(A1-1)+(S3-1);(A1-1)+(S3-2);(A1-1)+(S3-4);(A1-1)+(S3-7);(A1-1)+(S3-8);
(A1-1)+(S3-10);(A1-1)+(S3-11);(A1-1)+(S4-1);(A1-1)+(S4-5);
(A1-1)+(S4-6);(A1-1)+(S11-1);(A1-1)+(S11-2);(A1-1)+(S11-3);
(A1-1)+(S13-1);(A1-1)+(S13-2);(A1-1)+(S13-3);(A1-1)+(S13-8);
(A1-1)+(S14-1);(A1-1)+(S14-2);(A1-1)+(S14-3);(A1-2)+(S1-1);
(A1-2)+(S1-7);(A1-2)+(S1-11);(A1-2)+(S2-1);(A1-2)+(S3-1);
(A1-2)+(S3-2);(A1-2)+(S3-4);(A1-2)+(S3-7);(A1-2)+(S3-8);
(A1-2)+(S3-10);(A1-2)+(S3-11);(A1-2)+(S4-1);(A1-2)+(S4-5);
(A1-2)+(S4-6);(A1-2)+(S11-1);(A1-2)+(S11-2);(A1-2)+(S11-3);
(A1-2)+(S13-1);(A1-2)+(S13-2);(A1-2)+(S13-3);(A1-2)+(S13-8);
(A1-2)+(S14-1);(A1-2)+(S14-2);(A1-2)+(S14-3);(A1-3)+(S1-1);
(A1-3)+(S1-7);(A1-3)+(S1-11);(A1-3)+(S2-1);(A1-3)+(S3-1);
(A1-3)+(S3-2);(A1-3)+(S3-4);(A1-3)+(S3-7);(A1-3)+(S3-8);
(A1-3)+(S3-10);(A1-3)+(S3-11);(A1-3)+(S4-1);(A1-3)+(S4-5);
(A1-3)+(S4-6);(A1-3)+(S11-1);(A1-3)+(S11-2);(A1-3)+(S11-3);
(A1-3)+(S13-1);(A1-3)+(S13-2);(A1-3)+(S13-3);(A1-3)+(S13-8);
(A1-3)+(S14-1);(A1-3)+(S14-2);(A1-3)+(S14-3);(A1-4)+(S1-1);
(A1-4)+(S1-7);(A1-4)+(S1-11);(A1-4)+(S2-1);(A1-4)+(S3-1);
(A1-4)+(S3-2);(A1-4)+(S3-4);(A1-4)+(S3-7);(A1-4)+(S3-8);
(A1-4)+(S3-10);(A1-4)+(S3-11);(A1-4)+(S4-1);(A1-4)+(S4-5);
(A1-4)+(S4-6);(A1-4)+(S11-1);(A1-4)+(S11-2);(A1-4)+(S11-3);
(A1-4)+(S13-1);(A1-4)+(S13-2);(A1-4)+(S13-3);(A1-4)+(S13-8);
(A1-4)+(S14-1);(A1-4)+(S14-2);(A1-4)+(S14-3);(A1-5)+(S1-1);
(A1-5)+(S1-7);(A1-5)+(S1-11);(A1-5)+(S2-1);(A1-5)+(S3-1);
(A1-5)+(S3-2);(A1-5)+(S3-4);(A1-5)+(S3-7);(A1-5)+(S3-8);
(A1-5)+(S3-10);(A1-5)+(S3-11);(A1-5)+(S4-1);(A1-5)+(S4-5);
(A1-5)+(S4-6);(A1-5)+(S11-1);(A1-5)+(S11-2);(A1-5)+(S11-3);
(A1-5)+(S13-1);(A1-5)+(S13-2);(A1-5)+(S13-3);(A1-5)+(S13-8);
(A1-5)+(S14-1);(A1-5)+(S14-2);(A1-5)+(S14-3);(A1-6)+(S1-1);
(A1-6)+(S1-7);(A1-6)+(S1-11);(A1-6)+(S2-1);(A1-6)+(S3-1);
(A1-6)+(S3-2);(A1-6)+(S3-4);(A1-6)+(S3-7);(A1-6)+(S3-8);
(A1-6)+(S3-10);(A1-6)+(S3-11);(A1-6)+(S4-1);(A1-6)+(S4-5);
(A1-6)+(S4-6);(A1-6)+(S11-1);(A1-6)+(S11-2);(A1-6)+(S11-3);
(A1-6)+(S13-1);(A1-6)+(S13-2);(A1-6)+(S13-3);(A1-6)+(S13-8);
(A1-6)+(S14-1);(A1-6)+(S14-2);(A1-6)+(S14-3);(A1-7)+(S1-1);
(A1-7)+(S1-7);(A1-7)+(S1-11);(A1-7)+(S2-1);(A1-7)+(S3-1);
(A1-7)+(S3-2);(A1-7)+(S3-4);(A1-7)+(S3-7);(A1-7)+(S3-8);
(A1-7)+(S3-10);(A1-7)+(S3-11);(A1-7)+(S4-1);(A1-7)+(S4-5);
(A1-7)+(S4-6);(A1-7)+(S11-1);(A1-7)+(S11-2);(A1-7)+(S11-3);
(A1-7)+(S13-1);(A1-7)+(S13-2);(A1-7)+(S13-3);(A1-7)+(S13-8);
(A1-7)+(S14-1);(A1-7)+(S14-2);(A1-7)+(S14-3);(A1-8)+(S1-1);
(A1-8)+(S1-7);(A1-8)+(S1-11);(A1-8)+(S2-1);(A1-8)+(S3-1);
(A1-8)+(S3-2);(A1-8)+(S3-4);(A1-8)+(S3-7);(A1-8)+(S3-8);
(A1-8)+(S3-10);(A1-8)+(S3-11);(A1-8)+(S4-1);(A1-8)+(S4-5);
(A1-8)+(S4-6);(A1-8)+(S11-1);(A1-8)+(S11-2);(A1-8)+(S11-3);
(A1-8)+(S13-1);(A1-8)+(S13-2);(A1-8)+(S13-3);(A1-8)+(S13-8);
(A1-8)+(S14-1);(A1-8)+(S14-2);(A1-8)+(S14-3);(A1-9)+(S1-1);
(A1-9)+(S1-7);(A1-9)+(S1-11);(A1-9)+(S2-1);(A1-9)+(S3-1);
(A1-9)+(S3-2);(A1-9)+(S3-4);(A1-9)+(S3-7);(A1-9)+(S3-8);
(A1-9)+(S3-10);(A1-9)+(S3-11);(A1-9)+(S4-1);(A1-9)+(S4-5);
(A1-9)+(S4-6);(A1-9)+(S11-1);(A1-9)+(S11-2);(A1-9)+(S11-3);
(A1-9)+(S13-1);(A1-9)+(S13-2);(A1-9)+(S13-3);(A1-9)+(S13-8);
(A1-9)+(S14-1);(A1-9)+(S14-2);(A1-9)+(S14-3);(A1-10)+(S1-1);
(A1-10)+(S1-7);(A1-10)+(S1-11);(A1-10)+(S2-1);(A1-10)+(S3-1);
(A1-10)+(S3-2);(A1-10)+(S3-4);(A1-10)+(S3-7);(A1-10)+(S3-8);
(A1-10)+(S3-10);(A1-10)+(S3-11);(A1-10)+(S4-1);(A1-10)+(S4-5);
(A1-10)+(S4-6);(A1-10)+(S11-1);(A1-10)+(S11-2);(A1-10)+(S11-3);
(A1-10)+(S13-1);(A1-10)+(S13-2);(A1-10)+(S13-3);(A1-10)+(S13-8);
(A1-10)+(S14-1);(A1-10)+(S14-2);(A1-10)+(S14-3);(A1-11)+(S1-1);
(A1-11)+(S1-7);(A1-11)+(S1-11);(A1-11)+(S2-1);(A1-11)+(S3-1);
(A1-11)+(S3-2);(A1-11)+(S3-4);(A1-11)+(S3-7);(A1-11)+(S3-8);
(A1-11)+(S3-10);(A1-11)+(S3-11);(A1-11)+(S4-1);(A1-11)+(S4-5);
(A1-11)+(S4-6);(A1-11)+(S11-1);(A1-11)+(S11-2);(A1-11)+(S11-3);
(A1-11)+(S13-1);(A1-11)+(S13-2);(A1-11)+(S13-3);(A1-11)+(S13-8);
(A1-11)+(S14-1);(A1-11)+(S14-2);(A1-11)+(S14-3);(A1-12)+(S1-1);
(A1-12)+(S1-7);(A1-12)+(S1-11);(A1-12)+(S2-1);(A1-12)+(S3-1);
(A1-12)+(S3-2);(A1-12)+(S3-4);(A1-12)+(S3-7);(A1-12)+(S3-8);
(A1-12)+(S3-10);(A1-12)+(S3-11);(A1-12)+(S4-1);(A1-12)+(S4-5);
(A1-12)+(S4-6);(A1-12)+(S11-1);(A1-12)+(S11-2);(A1-12)+(S11-3);
(A1-12)+(S13-1);(A1-12)+(S13-2);(A1-12)+(S13-3);(A1-12)+(S13-8);
(A1-12)+(S14-1);(A1-12)+(S14-2);(A1-12)+(S14-3);(A1-13)+(S1-1);
(A1-13)+(S1-7);(A1-13)+(S1-11);(A1-13)+(S2-1);(A1-13)+(S3-1);
(A1-13)+(S3-2);(A1-13)+(S3-4);(A1-13)+(S3-7);(A1-13)+(S3-8);
(A1-13)+(S3-10);(A1-13)+(S3-11);(A1-13)+(S4-1);(A1-13)+(S4-5);
(A1-13)+(S4-6);(A1-13)+(S11-1);(A1-13)+(S11-2);(A1-13)+(S11-3);
(A1-13)+(S13-1);(A1-13)+(S13-2);(A1-13)+(S13-3);(A1-13)+(S13-8);
(A1-13)+(S14-1);(A1-13)+(S14-2);(A1-13)+(S14-3);(A1-14)+(S1-1);
(A1-14)+(S1-7);(A1-14)+(S1-11);(A1-14)+(S2-1);(A1-14)+(S3-1);
(A1-14)+(S3-2);(A1-14)+(S3-4);(A1-14)+(S3-7);(A1-14)+(S3-8);
(A1-14)+(S3-10);(A1-14)+(S3-11);(A1-14)+(S4-1);(A1-14)+(S4-5);
(A1-14)+(S4-6);(A1-14)+(S11-1);(A1-14)+(S11-2);(A1-14)+(S11-3);
(A1-14)+(S13-1);(A1-14)+(S13-2);(A1-14)+(S13-3);(A1-14)+(S13-8);
(A1-14)+(S14-1);(A1-14)+(S14-2);(A1-14)+(S14-3);(A1-15)+(S1-1);
(A1-15)+(S1-7);(A1-15)+(S1-11);(A1-15)+(S2-1);(A1-15)+(S3-1);
(A1-15)+(S3-2);(A1-15)+(S3-4);(A1-15)+(S3-7);(A1-15)+(S3-8);
(A1-15)+(S3-10);(A1-15)+(S3-11);(A1-15)+(S4-1);(A1-15)+(S4-5);
(A1-15)+(S4-6);(A1-15)+(S11-1);(A1-15)+(S11-2);(A1-15)+(S11-3);
(A1-15)+(S13-1);(A1-15)+(S13-2);(A1-15)+(S13-3);(A1-15)+(S13-8);
(A1-15)+(S14-1);(A1-15)+(S14-2);(A1-15)+(S14-3);(A1-16)+(S1-1);
(A1-16)+(S1-7);(A1-16)+(S1-11);(A1-16)+(S2-1);(A1-16)+(S3-1);
(A1-16)+(S3-2);(A1-16)+(S3-4);(A1-16)+(S3-7);(A1-16)+(S3-8);
(A1-16)+(S3-10);(A1-16)+(S3-11);(A1-16)+(S4-1);(A1-16)+(S4-5);
(A1-16)+(S4-6);(A1-16)+(S11-1);(A1-16)+(S11-2);(A1-16)+(S11-3);
(A1-16)+(S13-1);(A1-16)+(S13-2);(A1-16)+(S13-3);(A1-16)+(S13-8);
(A1-16)+(S14-1);(A1-16)+(S14-2);(A1-16)+(S14-3);(A1-17)+(S1-1);
(A1-17)+(S1-7);(A1-17)+(S1-11);(A1-17)+(S2-1);(A1-17)+(S3-1);
(A1-17)+(S3-2);(A1-17)+(S3-4);(A1-17)+(S3-7);(A1-17)+(S3-8);
(A1-17)+(S3-10);(A1-17)+(S3-11);(A1-17)+(S4-1);(A1-17)+(S4-5);
(A1-17)+(S4-6);(A1-17)+(S11-1);(A1-17)+(S11-2);(A1-17)+(S11-3);
(A1-17)+(S13-1);(A1-17)+(S13-2);(A1-17)+(S13-3);(A1-17)+(S13-8);
(A1-17)+(S14-1);(A1-17)+(S14-2);(A1-17)+(S14-3);(A1-18)+(S1-1);
(A1-18)+(S1-7);(A1-18)+(S1-11);(A1-18)+(S2-1);(A1-18)+(S3-1);
(A1-18)+(S3-2);(A1-18)+(S3-4);(A1-18)+(S3-7);(A1-18)+(S3-8);
(A1-18)+(S3-10);(A1-18)+(S3-11);(A1-18)+(S4-1);(A1-18)+(S4-5);
(A1-18)+(S4-6);(A1-18)+(S11-1);(A1-18)+(S11-2);(A1-18)+(S11-3);
(A1-18)+(S13-1);(A1-18)+(S13-2);(A1-18)+(S13-3);(A1-18)+(S13-8);
(A1-18)+(S14-1);(A1-18)+(S14-2);(A1-18)+(S14-3);(A1-19)+(S1-1);
(A1-19)+(S1-7);(A1-19)+(S1-11);(A1-19)+(S2-1);(A1-19)+(S3-1);
(A1-19)+(S3-2);(A1-19)+(S3-4);(A1-19)+(S3-7);(A1-19)+(S3-8);
(A1-19)+(S3-10);(A1-19)+(S3-11);(A1-19)+(S4-1);(A1-19)+(S4-5);
(A1-19)+(S4-6);(A1-19)+(S11-1);(A1-19)+(S11-2);(A1-19)+(S11-3);
(A1-19)+(S13-1);(A1-19)+(S13-2);(A1-19)+(S13-3);(A1-19)+(S13-8);
(A1-19)+(S14-1);(A1-19)+(S14-2);(A1-19)+(S14-3);(A1-20)+(S1-1);
(A1-20)+(S1-7);(A1-20)+(S1-11);(A1-20)+(S2-1);(A1-20)+(S3-1);
(A1-20)+(S3-2);(A1-20)+(S3-4);(A1-20)+(S3-7);(A1-20)+(S3-8);
(A1-20)+(S3-10);(A1-20)+(S3-11);(A1-20)+(S4-1);(A1-20)+(S4-5);
(A1-20)+(S4-6);(A1-20)+(S11-1);(A1-20)+(S11-2);(A1-20)+(S11-3);
(A1-20)+(S13-1);(A1-20)+(S13-2);(A1-20)+(S13-3);(A1-20)+(S13-8);
(A1-20)+(S14-1);(A1-20)+(S14-2);(A1-20)+(S14-3);(A1-21)+(S1-1);
(A1-21)+(S1-7);(A1-21)+(S1-11);(A1-21)+(S2-1);(A1-21)+(S3-1);
(A1-21)+(S3-2);(A1-21)+(S3-4);(A1-21)+(S3-7);(A1-21)+(S3-8);
(A1-21)+(S3-10);(A1-21)+(S3-11);(A1-21)+(S4-1);(A1-21)+(S4-5);
(A1-21)+(S4-6);(A1-21)+(S11-1);(A1-21)+(S11-2);(A1-21)+(S11-3);
(A1-21)+(S13-1);(A1-21)+(S13-2);(A1-21)+(S13-3);(A1-21)+(S13-8);
(A1-21)+(S14-1);(A1-21)+(S14-2);(A1-21)+(S14-3);(A1-22)+(S1-1);
(A1-22)+(S1-7);(A1-22)+(S1-11);(A1-22)+(S2-1);(A1-22)+(S3-1);
(A1-22)+(S3-2);(A1-22)+(S3-4);(A1-22)+(S3-7);(A1-22)+(S3-8);
(A1-22)+(S3-10);(A1-22)+(S3-11);(A1-22)+(S4-1);(A1-22)+(S4-5);
(A1-22)+(S4-6);(A1-22)+(S11-1);(A1-22)+(S11-2);(A1-22)+(S11-3);
(A1-22)+(S13-1);(A1-22)+(S13-2);(A1-22)+(S13-3);(A1-22)+(S13-8);
(A1-22)+(S14-1);(A1-22)+(S14-2);(A1-22)+(S14-3);(A1-23)+(S1-1);
(A1-23)+(S1-7);(A1-23)+(S1-11);(A1-23)+(S2-1);(A1-23)+(S3-1);
(A1-23)+(S3-2);(A1-23)+(S3-4);(A1-23)+(S3-7);(A1-23)+(S3-8);
(A1-23)+(S3-10);(A1-23)+(S3-11);(A1-23)+(S4-1);(A1-23)+(S4-5);
(A1-23)+(S4-6);(A1-23)+(S11-1);(A1-23)+(S11-2);(A1-23)+(S11-3);
(A1-23)+(S13-1);(A1-23)+(S13-2);(A1-23)+(S13-3);(A1-23)+(S13-8);
(A1-23)+(S14-1);(A1-23)+(S14-2);(A1-23)+(S14-3);(A1-24)+(S1-1);
(A1-24)+(S1-7);(A1-24)+(S1-11);(A1-24)+(S2-1);(A1-24)+(S3-1);
(A1-24)+(S3-2);(A1-24)+(S3-4);(A1-24)+(S3-7);(A1-24)+(S3-8);
(A1-24)+(S3-10);(A1-24)+(S3-11);(A1-24)+(S4-1);(A1-24)+(S4-5);
(A1-24)+(S4-6);(A1-24)+(S11-1);(A1-24)+(S11-2);(A1-24)+(S11-3);
(A1-24)+(S13-1);(A1-24)+(S13-2);(A1-24)+(S13-3);(A1-24)+(S13-8);
(A1-24)+(S14-1);(A1-24)+(S14-2);(A1-24)+(S14-3);(A1-25)+(S1-1);
(A1-25)+(S1-7);(A1-25)+(S1-11);(A1-25)+(S2-1);(A1-25)+(S3-1);
(A1-25)+(S3-2);(A1-25)+(S3-4);(A1-25)+(S3-7);(A1-25)+(S3-8);
(A1-25)+(S3-10);(A1-25)+(S3-11);(A1-25)+(S4-1);(A1-25)+(S4-5);
(A1-25)+(S4-6);(A1-25)+(S11-1);(A1-25)+(S11-2);(A1-25)+(S11-3);
(A1-25)+(S13-1);(A1-25)+(S13-2);(A1-25)+(S13-3);(A1-25)+(S13-8);
(A1-25)+(S14-1);(A1-25)+(S14-2);(A1-25)+(S14-3);(A1-26)+(S1-1);
(A1-26)+(S1-7);(A1-26)+(S1-11);(A1-26)+(S2-1);(A1-26)+(S3-1);
(A1-26)+(S3-2);(A1-26)+(S3-4);(A1-26)+(S3-7);(A1-26)+(S3-8);
(A1-26)+(S3-10);(A1-26)+(S3-11);(A1-26)+(S4-1);(A1-26)+(S4-5);
(A1-26)+(S4-6);(A1-26)+(S11-1);(A1-26)+(S11-2);(A1-26)+(S11-3);
(A1-26)+(S13-1);(A1-26)+(S13-2);(A1-26)+(S13-3);(A1-26)+(S13-8);
(A1-26)+(S14-1);(A1-26)+(S14-2);(A1-26)+(S14-3);(A1-27)+(S1-1);
(A1-27)+(S1-7);(A1-27)+(S1-11);(A1-27)+(S2-1);(A1-27)+(S3-1);
(A1-27)+(S3-2);(A1-27)+(S3-4);(A1-27)+(S3-7);(A1-27)+(S3-8);
(A1-27)+(S3-10);(A1-27)+(S3-11);(A1-27)+(S4-1);(A1-27)+(S4-5);
(A1-27)+(S4-6);(A1-27)+(S11-1);(A1-27)+(S11-2);(A1-27)+(S11-3);
(A1-27)+(S13-1);(A1-27)+(S13-2);(A1-27)+(S13-3);(A1-27)+(S13-8);
(A1-27)+(S14-1);(A1-27)+(S14-2);(A1-27)+(S14-3);(A1-28)+(S1-1);
(A1-28)+(S1-7);(A1-28)+(S1-11);(A1-28)+(S2-1);(A1-28)+(S3-1);
(A1-28)+(S3-2);(A1-28)+(S3-4);(A1-28)+(S3-7);(A1-28)+(S3-8);
(A1-28)+(S3-10);(A1-28)+(S3-11);(A1-28)+(S4-1);(A1-28)+(S4-5);
(A1-28)+(S4-6);(A1-28)+(S11-1);(A1-28)+(S11-2);(A1-28)+(S11-3);
(A1-28)+(S13-1);(A1-28)+(S13-2);(A1-28)+(S13-3);(A1-28)+(S13-8);
(A1-28)+(S14-1);(A1-28)+(S14-2);(A1-28)+(S14-3);(A1-29)+(S1-1);
(A1-29)+(S1-7);(A1-29)+(S1-11);(A1-29)+(S2-1);(A1-29)+(S3-1);
(A1-29)+(S3-2);(A1-29)+(S3-4);(A1-29)+(S3-7);(A1-29)+(S3-8);
(A1-29)+(S3-10);(A1-29)+(S3-11);(A1-29)+(S4-1);(A1-29)+(S4-5);
(A1-29)+(S4-6);(A1-29)+(S11-1);(A1-29)+(S11-2);(A1-29)+(S11-3);
(A1-29)+(S13-1);(A1-29)+(S13-2);(A1-29)+(S13-3);(A1-29)+(S13-8);
(A1-29)+(S14-1);(A1-29)+(S14-2);(A1-29)+(S14-3);(A1-30)+(S1-1);
(A1-30)+(S1-7);(A1-30)+(S1-11);(A1-30)+(S2-1);(A1-30)+(S3-1);
(A1-30)+(S3-2);(A1-30)+(S3-4);(A1-30)+(S3-7);(A1-30)+(S3-8);
(A1-30)+(S3-10);(A1-30)+(S3-11);(A1-30)+(S4-1);(A1-30)+(S4-5);
(A1-30)+(S4-6);(A1-30)+(S11-1);(A1-30)+(S11-2);(A1-30)+(S11-3);
(A1-30)+(S13-1);(A1-30)+(S13-2);(A1-30)+(S13-3);(A1-30)+(S13-8);
(A1-30)+(S14-1);(A1-30)+(S14-2);(A1-30)+(S14-3);(A1-31)+(S1-1);
(A1-31)+(S1-7);(A1-31)+(S1-11);(A1-31)+(S2-1);(A1-31)+(S3-1);
(A1-31)+(S3-2);(A1-31)+(S3-4);(A1-31)+(S3-7);(A1-31)+(S3-8);
(A1-31)+(S3-10);(A1-31)+(S3-11);(A1-31)+(S4-1);(A1-31)+(S4-5);
(A1-31)+(S4-6);(A1-31)+(S11-1);(A1-31)+(S11-2);(A1-31)+(S11-3);
(A1-31)+(S13-1);(A1-31)+(S13-2);(A1-31)+(S13-3);(A1-31)+(S13-8);
(A1-31)+(S14-1);(A1-31)+(S14-2);(A1-31)+(S14-3);(A1-32)+(S1-1);
(A1-32)+(S1-7);(A1-32)+(S1-11);(A1-32)+(S2-1);(A1-32)+(S3-1);
(A1-32)+(S3-2);(A1-32)+(S3-4);(A1-32)+(S3-7);(A1-32)+(S3-8);
(A1-32)+(S3-10);(A1-32)+(S3-11);(A1-32)+(S4-1);(A1-32)+(S4-5);
(A1-32)+(S4-6);(A1-32)+(S11-1);(A1-32)+(S11-2);(A1-32)+(S11-3);
(A1-32)+(S13-1);(A1-32)+(S13-2);(A1-32)+(S13-3);(A1-32)+(S13-8);
(A1-32)+(S14-1);(A1-32)+(S14-2);(A1-32)+(S14-3);(A1-33)+(S1-1);
(A1-33)+(S1-7);(A1-33)+(S1-11);(A1-33)+(S2-1);(A1-33)+(S3-1);
(A1-33)+(S3-2);(A1-33)+(S3-4);(A1-33)+(S3-7);(A1-33)+(S3-8);
(A1-33)+(S3-10);(A1-33)+(S3-11);(A1-33)+(S4-1);(A1-33)+(S4-5);
(A1-33)+(S4-6);(A1-33)+(S11-1);(A1-33)+(S11-2);(A1-33)+(S11-3);
(A1-33)+(S13-1);(A1-33)+(S13-2);(A1-33)+(S13-3);(A1-33)+(S13-8);
(A1-33)+(S14-1);(A1-33)+(S14-2);(A1-33)+(S14-3);(A1-34)+(S1-1);
(A1-34)+(S1-7);(A1-34)+(S1-11);(A1-34)+(S2-1);(A1-34)+(S3-1);
(A1-34)+(S3-2);(A1-34)+(S3-4);(A1-34)+(S3-7);(A1-34)+(S3-8);
(A1-34)+(S3-10);(A1-34)+(S3-11);(A1-34)+(S4-1);(A1-34)+(S4-5);
(A1-34)+(S4-6);(A1-34)+(S11-1);(A1-34)+(S11-2);(A1-34)+(S11-3);
(A1-34)+(S13-1);(A1-34)+(S13-2);(A1-34)+(S13-3);(A1-34)+(S13-8);
(A1-34)+(S14-1);(A1-34)+(S14-2);(A1-34)+(S14-3);(A1-35)+(S1-1);
(A1-35)+(S1-7);(A1-35)+(S1-11);(A1-35)+(S2-1);(A1-35)+(S3-1);
(A1-35)+(S3-2);(A1-35)+(S3-4);(A1-35)+(S3-7);(A1-35)+(S3-8);
(A1-35)+(S3-10);(A1-35)+(S3-11);(A1-35)+(S4-1);(A1-35)+(S4-5);
(A1-35)+(S4-6);(A1-35)+(S11-1);(A1-35)+(S11-2);(A1-35)+(S11-3);
(A1-35)+(S13-1);(A1-35)+(S13-2);(A1-35)+(S13-3);(A1-35)+(S13-8);
(A1-35)+(S14-1);(A1-35)+(S14-2);(A1-35)+(S14-3);(A1-36)+(S1-1);
(A1-36)+(S1-7);(A1-36)+(S1-11);(A1-36)+(S2-1);(A1-36)+(S3-1);
(A1-36)+(S3-2);(A1-36)+(S3-4);(A1-36)+(S3-7);(A1-36)+(S3-8);
(A1-36)+(S3-10);(A1-36)+(S3-11);(A1-36)+(S4-1);(A1-36)+(S4-5);
(A1-36)+(S4-6);(A1-36)+(S11-1);(A1-36)+(S11-2);(A1-36)+(S11-3);
(A1-36)+(S13-1);(A1-36)+(S13-2);(A1-36)+(S13-3);(A1-36)+(S13-8);
(A1-36)+(S14-1);(A1-36)+(S14-2);(A1-36)+(S14-3);(A1-37)+(S1-1);
(A1-37)+(S1-7);(A1-37)+(S1-11);(A1-37)+(S2-1);(A1-37)+(S3-1);
(A1-37)+(S3-2);(A1-37)+(S3-4);(A1-37)+(S3-7);(A1-37)+(S3-8);
(A1-37)+(S3-10);(A1-37)+(S3-11);(A1-37)+(S4-1);(A1-37)+(S4-5);
(A1-37)+(S4-6);(A1-37)+(S11-1);(A1-37)+(S11-2);(A1-37)+(S11-3);
(A1-37)+(S13-1);(A1-37)+(S13-2);(A1-37)+(S13-3);(A1-37)+(S13-8);
(A1-37)+(S14-1);(A1-37)+(S14-2);(A1-37)+(S14-3);(A1-38)+(S1-1);
(A1-38)+(S1-7);(A1-38)+(S1-11);(A1-38)+(S2-1);(A1-38)+(S3-1);
(A1-38)+(S3-2);(A1-38)+(S3-4);(A1-38)+(S3-7);(A1-38)+(S3-8);
(A1-38)+(S3-10);(A1-38)+(S3-11);(A1-38)+(S4-1);(A1-38)+(S4-5);
(A1-38)+(S4-6);(A1-38)+(S11-1);(A1-38)+(S11-2);(A1-38)+(S11-3);
(A1-38)+(S13-1);(A1-38)+(S13-2);(A1-38)+(S13-3);(A1-38)+(S13-8);
(A1-38)+(S14-1);(A1-38)+(S14-2);(A1-38)+(S14-3);(A1-39)+(S1-1);
(A1-39)+(S1-7);(A1-39)+(S1-11);(A1-39)+(S2-1);(A1-39)+(S3-1);
(A1-39)+(S3-2);(A1-39)+(S3-4);(A1-39)+(S3-7);(A1-39)+(S3-8);
(A1-39)+(S3-10);(A1-39)+(S3-11);(A1-39)+(S4-1);(A1-39)+(S4-5);
(A1-39)+(S4-6);(A1-39)+(S11-1);(A1-39)+(S11-2);(A1-39)+(S11-3);
(A1-39)+(S13-1);(A1-39)+(S13-2);(A1-39)+(S13-3);(A1-39)+(S13-8);
(A1-39)+(S14-1);(A1-39)+(S14-2);(A1-39)+(S14-3);(A1-40)+(S1-1);
(A1-40)+(S1-7);(A1-40)+(S1-11);(A1-40)+(S2-1);(A1-40)+(S3-1);
(A1-40)+(S3-2);(A1-40)+(S3-4);(A1-40)+(S3-7);(A1-40)+(S3-8);
(A1-40)+(S3-10);(A1-40)+(S3-11);(A1-40)+(S4-1);(A1-40)+(S4-5);
(A1-40)+(S4-6);(A1-40)+(S11-1);(A1-40)+(S11-2);(A1-40)+(S11-3);
(A1-40)+(S13-1);(A1-40)+(S13-2);(A1-40)+(S13-3);(A1-40)+(S13-8);
(A1-40)+(S14-1);(A1-40)+(S14-2);(A1-40)+(S14-3);(A1-41)+(S1-1);
(A1-41)+(S1-7);(A1-41)+(S1-11);(A1-41)+(S2-1);(A1-41)+(S3-1);
(A1-41)+(S3-2);(A1-41)+(S3-4);(A1-41)+(S3-7);(A1-41)+(S3-8);
(A1-41)+(S3-10);(A1-41)+(S3-11);(A1-41)+(S4-1);(A1-41)+(S4-5);
(A1-41)+(S4-6);(A1-41)+(S11-1);(A1-41)+(S11-2);(A1-41)+(S11-3);
(A1-41)+(S13-1);(A1-41)+(S13-2);(A1-41)+(S13-3);(A1-41)+(S13-8);
(A1-41)+(S14-1);(A1-41)+(S14-2);(A1-41)+(S14-3);(A1-42)+(S1-1);
(A1-42)+(S1-7);(A1-42)+(S1-11);(A1-42)+(S2-1);(A1-42)+(S3-1);
(A1-42)+(S3-2);(A1-42)+(S3-4);(A1-42)+(S3-7);(A1-42)+(S3-8);
(A1-42)+(S3-10);(A1-42)+(S3-11);(A1-42)+(S4-1);(A1-42)+(S4-5);
(A1-42)+(S4-6);(A1-42)+(S11-1);(A1-42)+(S11-2);(A1-42)+(S11-3);
(A1-42)+(S13-1);(A1-42)+(S13-2);(A1-42)+(S13-3);(A1-42)+(S13-8);
(A1-42)+(S14-1);(A1-42)+(S14-2);(A1-42)+(S14-3);(A1-43)+(S1-1);
(A1-43)+(S1-7);(A1-43)+(S1-11);(A1-43)+(S2-1);(A1-43)+(S3-1);
(A1-43)+(S3-2);(A1-43)+(S3-4);(A1-43)+(S3-7);(A1-43)+(S3-8);
(A1-43)+(S3-10);(A1-43)+(S3-11);(A1-43)+(S4-1);(A1-43)+(S4-5);
(A1-43)+(S4-6);(A1-43)+(S11-1);(A1-43)+(S11-2);(A1-43)+(S11-3);
(A1-43)+(S13-1);(A1-43)+(S13-2);(A1-43)+(S13-3);(A1-43)+(S13-8);
(A1-43)+(S14-1);(A1-43)+(S14-2);(A1-43)+(S14-3);(A1-44)+(S1-1);
(A1-44)+(S1-7);(A1-44)+(S1-11);(A1-44)+(S2-1);(A1-44)+(S3-1);
(A1-44)+(S3-2);(A1-44)+(S3-4);(A1-44)+(S3-7);(A1-44)+(S3-8);
(A1-44)+(S3-10);(A1-44)+(S3-11);(A1-44)+(S4-1);(A1-44)+(S4-5);
(A1-44)+(S4-6);(A1-44)+(S11-1);(A1-44)+(S11-2);(A1-44)+(S11-3);
(A1-44)+(S13-1);(A1-44)+(S13-2);(A1-44)+(S13-3);(A1-44)+(S13-8);
(A1-44)+(S14-1);(A1-44)+(S14-2);(A1-44)+(S14-3);(A1-45)+(S1-1);
(A1-45)+(S1-7);(A1-45)+(S1-11);(A1-45)+(S2-1);(A1-45)+(S3-1);
(A1-45)+(S3-2);(A1-45)+(S3-4);(A1-45)+(S3-7);(A1-45)+(S3-8);
(A1-45)+(S3-10);(A1-45)+(S3-11);(A1-45)+(S4-1);(A1-45)+(S4-5);
(A1-45)+(S4-6);(A1-45)+(S11-1);(A1-45)+(S11-2);(A1-45)+(S11-3);
(A1-45)+(S13-1);(A1-45)+(S13-2);(A1-45)+(S13-3);(A1-45)+(S13-8);
(A1-45)+(S14-1);(A1-45)+(S14-2);(A1-45)+(S14-3);(A1-46)+(S1-1);
(A1-46)+(S1-7);(A1-46)+(S1-11);(A1-46)+(S2-1);(A1-46)+(S3-1);
(A1-46)+(S3-2);(A1-46)+(S3-4);(A1-46)+(S3-7);(A1-46)+(S3-8);
(A1-46)+(S3-10);(A1-46)+(S3-11);(A1-46)+(S4-1);(A1-46)+(S4-5);
(A1-46)+(S4-6);(A1-46)+(S11-1);(A1-46)+(S11-2);(A1-46)+(S11-3);
(A1-46)+(S13-1);(A1-46)+(S13-2);(A1-46)+(S13-3);(A1-46)+(S13-8);
(A1-46)+(S14-1);(A1-46)+(S14-2);(A1-46)+(S14-3);(A1-47)+(S1-1);
(A1-47)+(S1-7);(A1-47)+(S1-11);(A1-47)+(S2-1);(A1-47)+(S3-1);
(A1-47)+(S3-2);(A1-47)+(S3-4);(A1-47)+(S3-7);(A1-47)+(S3-8);
(A1-47)+(S3-10);(A1-47)+(S3-11);(A1-47)+(S4-1);(A1-47)+(S4-5);
(A1-47)+(S4-6);(A1-47)+(S11-1);(A1-47)+(S11-2);(A1-47)+(S11-3);
(A1-47)+(S13-1);(A1-47)+(S13-2);(A1-47)+(S13-3);(A1-47)+(S13-8);
(A1-47)+(S14-1);(A1-47)+(S14-2);(A1-47)+(S14-3);(A1-48)+(S1-1);
(A1-48)+(S1-7);(A1-48)+(S1-11);(A1-48)+(S2-1);(A1-48)+(S3-1);
(A1-48)+(S3-2);(A1-48)+(S3-4);(A1-48)+(S3-7);(A1-48)+(S3-8);
(A1-48)+(S3-10);(A1-48)+(S3-11);(A1-48)+(S4-1);(A1-48)+(S4-5);
(A1-48)+(S4-6);(A1-48)+(S11-1);(A1-48)+(S11-2);(A1-48)+(S11-3);
(A1-48)+(S13-1);(A1-48)+(S13-2);(A1-48)+(S13-3);(A1-48)+(S13-8);
(A1-48)+(S14-1);(A1-48)+(S14-2);(A1-48)+(S14-3);(A1-49)+(S1-1);
(A1-49)+(S1-7);(A1-49)+(S1-11);(A1-49)+(S2-1);(A1-49)+(S3-1);
(A1-49)+(S3-2);(A1-49)+(S3-4);(A1-49)+(S3-7);(A1-49)+(S3-8);
(A1-49)+(S3-10);(A1-49)+(S3-11);(A1-49)+(S4-1);(A1-49)+(S4-5);
(A1-49)+(S4-6);(A1-49)+(S11-1);(A1-49)+(S11-2);(A1-49)+(S11-3);
(A1-49)+(S13-1);(A1-49)+(S13-2);(A1-49)+(S13-3);(A1-49)+(S13-8);
(A1-49)+(S14-1);(A1-49)+(S14-2);(A1-49)+(S14-3);(A1-50)+(S1-1);
(A1-50)+(S1-7);(A1-50)+(S1-11);(A1-50)+(S2-1);(A1-50)+(S3-1);
(A1-50)+(S3-2);(A1-50)+(S3-4);(A1-50)+(S3-7);(A1-50)+(S3-8);
(A1-50)+(S3-10);(A1-50)+(S3-11);(A1-50)+(S4-1);(A1-50)+(S4-5);
(A1-50)+(S4-6);(A1-50)+(S11-1);(A1-50)+(S11-2);(A1-50)+(S11-3);
(A1-50)+(S13-1);(A1-50)+(S13-2);(A1-50)+(S13-3);(A1-50)+(S13-8);
(A1-50)+(S14-1);(A1-50)+(S14-2);(A1-50)+(S14-3);(A1-51)+(S1-1);
(A1-51)+(S1-7);(A1-51)+(S1-11);(A1-51)+(S2-1);(A1-51)+(S3-1);
(A1-51)+(S3-2);(A1-51)+(S3-4);(A1-51)+(S3-7);(A1-51)+(S3-8);
(A1-51)+(S3-10);(A1-51)+(S3-11);(A1-51)+(S4-1);(A1-51)+(S4-5);
(A1-51)+(S4-6);(A1-51)+(S11-1);(A1-51)+(S11-2);(A1-51)+(S11-3);
(A1-51)+(S13-1);(A1-51)+(S13-2);(A1-51)+(S13-3);(A1-51)+(S13-8);
(A1-51)+(S14-1);(A1-51)+(S14-2);(A1-51)+(S14-3);(A1-52)+(S1-1);
(A1-52)+(S1-7);(A1-52)+(S1-11);(A1-52)+(S2-1);(A1-52)+(S3-1);
(A1-52)+(S3-2);(A1-52)+(S3-4);(A1-52)+(S3-7);(A1-52)+(S3-8);
(A1-52)+(S3-10);(A1-52)+(S3-11);(A1-52)+(S4-1);(A1-52)+(S4-5);
(A1-52)+(S4-6);(A1-52)+(S11-1);(A1-52)+(S11-2);(A1-52)+(S11-3);
(A1-52)+(S13-1);(A1-52)+(S13-2);(A1-52)+(S13-3);(A1-52)+(S13-8);
(A1-52)+(S14-1);(A1-52)+(S14-2);(A1-52)+(S14-3);(A1-53)+(S1-1);
(A1-53)+(S1-7);(A1-53)+(S1-11);(A1-53)+(S2-1);(A1-53)+(S3-1);
(A1-53)+(S3-2);(A1-53)+(S3-4);(A1-53)+(S3-7);(A1-53)+(S3-8);
(A1-53)+(S3-10);(A1-53)+(S3-11);(A1-53)+(S4-1);(A1-53)+(S4-5);
(A1-53)+(S4-6);(A1-53)+(S11-1);(A1-53)+(S11-2);(A1-53)+(S11-3);
(A1-53)+(S13-1);(A1-53)+(S13-2);(A1-53)+(S13-3);(A1-53)+(S13-8);
(A1-53)+(S14-1);(A1-53)+(S14-2);(A1-53)+(S14-3);(A1-54)+(S1-1);
(A1-54)+(S1-7);(A1-54)+(S1-11);(A1-54)+(S2-1);(A1-54)+(S3-1);
(A1-54)+(S3-2);(A1-54)+(S3-4);(A1-54)+(S3-7);(A1-54)+(S3-8);
(A1-54)+(S3-10);(A1-54)+(S3-11);(A1-54)+(S4-1);(A1-54)+(S4-5);
(A1-54)+(S4-6);(A1-54)+(S11-1);(A1-54)+(S11-2);(A1-54)+(S11-3);
(A1-54)+(S13-1);(A1-54)+(S13-2);(A1-54)+(S13-3);(A1-54)+(S13-8);
(A1-54)+(S14-1);(A1-54)+(S14-2);(A1-54)+(S14-3);(A1-55)+(S1-1);
(A1-55)+(S1-7);(A1-55)+(S1-11);(A1-55)+(S2-1);(A1-55)+(S3-1);
(A1-55)+(S3-2);(A1-55)+(S3-4);(A1-55)+(S3-7);(A1-55)+(S3-8);
(A1-55)+(S3-10);(A1-55)+(S3-11);(A1-55)+(S4-1);(A1-55)+(S4-5);
(A1-55)+(S4-6);(A1-55)+(S11-1);(A1-55)+(S11-2);(A1-55)+(S11-3);
(A1-55)+(S13-1);(A1-55)+(S13-2);(A1-55)+(S13-3);(A1-55)+(S13-8);
(A1-55)+(S14-1);(A1-55)+(S14-2);(A1-55)+(S14-3);(A1-56)+(S1-1);
(A1-56)+(S1-7);(A1-56)+(S1-11);(A1-56)+(S2-1);(A1-56)+(S3-1);
(A1-56)+(S3-2);(A1-56)+(S3-4);(A1-56)+(S3-7);(A1-56)+(S3-8);
(A1-56)+(S3-10);(A1-56)+(S3-11);(A1-56)+(S4-1);(A1-56)+(S4-5);
(A1-56)+(S4-6);(A1-56)+(S11-1);(A1-56)+(S11-2);(A1-56)+(S11-3);
(A1-56)+(S13-1);(A1-56)+(S13-2);(A1-56)+(S13-3);(A1-56)+(S13-8);
(A1-56)+(S14-1);(A1-56)+(S14-2);(A1-56)+(S14-3);(A1-57)+(S1-1);
(A1-57)+(S1-7);(A1-57)+(S1-11);(A1-57)+(S2-1);(A1-57)+(S3-1);
(A1-57)+(S3-2);(A1-57)+(S3-4);(A1-57)+(S3-7);(A1-57)+(S3-8);
(A1-57)+(S3-10);(A1-57)+(S3-11);(A1-57)+(S4-1);(A1-57)+(S4-5);
(A1-57)+(S4-6);(A1-57)+(S11-1);(A1-57)+(S11-2);(A1-57)+(S11-3);
(A1-57)+(S13-1);(A1-57)+(S13-2);(A1-57)+(S13-3);(A1-57)+(S13-8);
(A1-57)+(S14-1);(A1-57)+(S14-2);(A1-57)+(S14-3);(A1-58)+(S1-1);
(A1-58)+(S1-7);(A1-58)+(S1-11);(A1-58)+(S2-1);(A1-58)+(S3-1);
(A1-58)+(S3-2);(A1-58)+(S3-4);(A1-58)+(S3-7);(A1-58)+(S3-8);
(A1-58)+(S3-10);(A1-58)+(S3-11);(A1-58)+(S4-1);(A1-58)+(S4-5);
(A1-58)+(S4-6);(A1-58)+(S11-1);(A1-58)+(S11-2);(A1-58)+(S11-3);
(A1-58)+(S13-1);(A1-58)+(S13-2);(A1-58)+(S13-3);(A1-58)+(S13-8);
(A1-58)+(S14-1);(A1-58)+(S14-2);(A1-58)+(S14-3);(A1-59)+(S1-1);
(A1-59)+(S1-7);(A1-59)+(S1-11);(A1-59)+(S2-1);(A1-59)+(S3-1);
(A1-59)+(S3-2);(A1-59)+(S3-4);(A1-59)+(S3-7);(A1-59)+(S3-8);
(A1-59)+(S3-10);(A1-59)+(S3-11);(A1-59)+(S4-1);(A1-59)+(S4-5);
(A1-59)+(S4-6);(A1-59)+(S11-1);(A1-59)+(S11-2);(A1-59)+(S11-3);
(A1-59)+(S13-1);(A1-59)+(S13-2);(A1-59)+(S13-3);(A1-59)+(S13-8);
(A1-59)+(S14-1);(A1-59)+(S14-2);(A1-59)+(S14-3);(A1-60)+(S1-1);
(A1-60)+(S1-7);(A1-60)+(S1-11);(A1-60)+(S2-1);(A1-60)+(S3-1);
(A1-60)+(S3-2);(A1-60)+(S3-4);(A1-60)+(S3-7);(A1-60)+(S3-8);
(A1-60)+(S3-10);(A1-60)+(S3-11);(A1-60)+(S4-1);(A1-60)+(S4-5);
(A1-60)+(S4-6);(A1-60)+(S11-1);(A1-60)+(S11-2);(A1-60)+(S11-3);
(A1-60)+(S13-1);(A1-60)+(S13-2);(A1-60)+(S13-3);(A1-60)+(S13-8);
(A1-60)+(S14-1);(A1-60)+(S14-2);(A1-60)+(S14-3);(A1-61)+(S1-1);
(A1-61)+(S1-7);(A1-61)+(S1-11);(A1-61)+(S2-1);(A1-61)+(S3-1);
(A1-61)+(S3-2);(A1-61)+(S3-4);(A1-61)+(S3-7);(A1-61)+(S3-8);
(A1-61)+(S3-10);(A1-61)+(S3-11);(A1-61)+(S4-1);(A1-61)+(S4-5);
(A1-61)+(S4-6);(A1-61)+(S11-1);(A1-61)+(S11-2);(A1-61)+(S11-3);
(A1-61)+(S13-1);(A1-61)+(S13-2);(A1-61)+(S13-3);(A1-61)+(S13-8);
(A1-61)+(S14-1);(A1-61)+(S14-2);(A1-61)+(S14-3);(A1-62)+(S1-1);
(A1-62)+(S1-7);(A1-62)+(S1-11);(A1-62)+(S2-1);(A1-62)+(S3-1);
(A1-62)+(S3-2);(A1-62)+(S3-4);(A1-62)+(S3-7);(A1-62)+(S3-8);
(A1-62)+(S3-10);(A1-62)+(S3-11);(A1-62)+(S4-1);(A1-62)+(S4-5);
(A1-62)+(S4-6);(A1-62)+(S11-1);(A1-62)+(S11-2);(A1-62)+(S11-3);
(A1-62)+(S13-1);(A1-62)+(S13-2);(A1-62)+(S13-3);(A1-62)+(S13-8);
(A1-62)+(S14-1);(A1-62)+(S14-2);(A1-62)+(S14-3);(A1-63)+(S1-1);
(A1-63)+(S1-7);(A1-63)+(S1-11);(A1-63)+(S2-1);(A1-63)+(S3-1);
(A1-63)+(S3-2);(A1-63)+(S3-4);(A1-63)+(S3-7);(A1-63)+(S3-8);
(A1-63)+(S3-10);(A1-63)+(S3-11);(A1-63)+(S4-1);(A1-63)+(S4-5);
(A1-63)+(S4-6);(A1-63)+(S11-1);(A1-63)+(S11-2);(A1-63)+(S11-3);
(A1-63)+(S13-1);(A1-63)+(S13-2);(A1-63)+(S13-3);(A1-63)+(S13-8);
(A1-63)+(S14-1);(A1-63)+(S14-2);(A1-63)+(S14-3);(A1-64)+(S1-1);
(A1-64)+(S1-7);(A1-64)+(S1-11);(A1-64)+(S2-1);(A1-64)+(S3-1);
(A1-64)+(S3-2);(A1-64)+(S3-4);(A1-64)+(S3-7);(A1-64)+(S3-8);
(A1-64)+(S3-10);(A1-64)+(S3-11);(A1-64)+(S4-1);(A1-64)+(S4-5);
(A1-64)+(S4-6);(A1-64)+(S11-1);(A1-64)+(S11-2);(A1-64)+(S11-3);
(A1-64)+(S13-1);(A1-64)+(S13-2);(A1-64)+(S13-3);(A1-64)+(S13-8);
(A1-64)+(S14-1);(A1-64)+(S14-2);(A1-64)+(S14-3);(A1-65)+(S1-1);
(A1-65)+(S1-7);(A1-65)+(S1-11);(A1-65)+(S2-1);(A1-65)+(S3-1);
(A1-65)+(S3-2);(A1-65)+(S3-4);(A1-65)+(S3-7);(A1-65)+(S3-8);
(A1-65)+(S3-10);(A1-65)+(S3-11);(A1-65)+(S4-1);(A1-65)+(S4-5);
(A1-65)+(S4-6);(A1-65)+(S11-1);(A1-65)+(S11-2);(A1-65)+(S11-3);
(A1-65)+(S13-1);(A1-65)+(S13-2);(A1-65)+(S13-3);(A1-65)+(S13-8);
(A1-65)+(S14-1);(A1-65)+(S14-2);(A1-65)+(S14-3);(A1-66)+(S1-1);
(A1-66)+(S1-7);(A1-66)+(S1-11);(A1-66)+(S2-1);(A1-66)+(S3-1);
(A1-66)+(S3-2);(A1-66)+(S3-4);(A1-66)+(S3-7);(A1-66)+(S3-8);
(A1-66)+(S3-10);(A1-66)+(S3-11);(A1-66)+(S4-1);(A1-66)+(S4-5);
(A1-66)+(S4-6);(A1-66)+(S11-1);(A1-66)+(S11-2);(A1-66)+(S11-3);
(A1-66)+(S13-1);(A1-66)+(S13-2);(A1-66)+(S13-3);(A1-66)+(S13-8);
(A1-66)+(S14-1);(A1-66)+(S14-2);(A1-66)+(S14-3);(A1-67)+(S1-1);
(A1-67)+(S1-7);(A1-67)+(S1-11);(A1-67)+(S2-1);(A1-67)+(S3-1);
(A1-67)+(S3-2);(A1-67)+(S3-4);(A1-67)+(S3-7);(A1-67)+(S3-8);
(A1-67)+(S3-10);(A1-67)+(S3-11);(A1-67)+(S4-1);(A1-67)+(S4-5);
(A1-67)+(S4-6);(A1-67)+(S11-1);(A1-67)+(S11-2);(A1-67)+(S11-3);
(A1-67)+(S13-1);(A1-67)+(S13-2);(A1-67)+(S13-3);(A1-67)+(S13-8);
(A1-67)+(S14-1);(A1-67)+(S14-2);(A1-67)+(S14-3);(A1-68)+(S1-1);
(A1-68)+(S1-7);(A1-68)+(S1-11);(A1-68)+(S2-1);(A1-68)+(S3-1);
(A1-68)+(S3-2);(A1-68)+(S3-4);(A1-68)+(S3-7);(A1-68)+(S3-8);
(A1-68)+(S3-10);(A1-68)+(S3-11);(A1-68)+(S4-1);(A1-68)+(S4-5);
(A1-68)+(S4-6);(A1-68)+(S11-1);(A1-68)+(S11-2);(A1-68)+(S11-3);
(A1-68)+(S13-1);(A1-68)+(S13-2);(A1-68)+(S13-3);(A1-68)+(S13-8);
(A1-68)+(S14-1);(A1-68)+(S14-2);(A1-68)+(S14-3);(A1-69)+(S1-1);
(A1-69)+(S1-7);(A1-69)+(S1-11);(A1-69)+(S2-1);(A1-69)+(S3-1);
(A1-69)+(S3-2);(A1-69)+(S3-4);(A1-69)+(S3-7);(A1-69)+(S3-8);
(A1-69)+(S3-10);(A1-69)+(S3-11);(A1-69)+(S4-1);(A1-69)+(S4-5);
(A1-69)+(S4-6);(A1-69)+(S11-1);(A1-69)+(S11-2);(A1-69)+(S11-3);
(A1-69)+(S13-1);(A1-69)+(S13-2);(A1-69)+(S13-3);(A1-69)+(S13-8);
(A1-69)+(S14-1);(A1-69)+(S14-2);(A1-69)+(S14-3);(A1-70)+(S1-1);
(A1-70)+(S1-7);(A1-70)+(S1-11);(A1-70)+(S2-1);(A1-70)+(S3-1);
(A1-70)+(S3-2);(A1-70)+(S3-4);(A1-70)+(S3-7);(A1-70)+(S3-8);
(A1-70)+(S3-10);(A1-70)+(S3-11);(A1-70)+(S4-1);(A1-70)+(S4-5);
(A1-70)+(S4-6);(A1-70)+(S11-1);(A1-70)+(S11-2);(A1-70)+(S11-3);
(A1-70)+(S13-1);(A1-70)+(S13-2);(A1-70)+(S13-3);(A1-70)+(S13-8);
(A1-70)+(S14-1);(A1-70)+(S14-2);(A1-70)+(S14-3);(A1-71)+(S1-1);
(A1-71)+(S1-7);(A1-71)+(S1-11);(A1-71)+(S2-1);(A1-71)+(S3-1);
(A1-71)+(S3-2);(A1-71)+(S3-4);(A1-71)+(S3-7);(A1-71)+(S3-8);
(A1-71)+(S3-10);(A1-71)+(S3-11);(A1-71)+(S4-1);(A1-71)+(S4-5);
(A1-71)+(S4-6);(A1-71)+(S11-1);(A1-71)+(S11-2);(A1-71)+(S11-3);
(A1-71)+(S13-1);(A1-71)+(S13-2);(A1-71)+(S13-3);(A1-71)+(S13-8);
(A1-71)+(S14-1);(A1-71)+(S14-2);(A1-71)+(S14-3);(A1-72)+(S1-1);
(A1-72)+(S1-7);(A1-72)+(S1-11);(A1-72)+(S2-1);(A1-72)+(S3-1);
(A1-72)+(S3-2);(A1-72)+(S3-4);(A1-72)+(S3-7);(A1-72)+(S3-8);
(A1-72)+(S3-10);(A1-72)+(S3-11);(A1-72)+(S4-1);(A1-72)+(S4-5);
(A1-72)+(S4-6);(A1-72)+(S11-1);(A1-72)+(S11-2);(A1-72)+(S11-3);
(A1-72)+(S13-1);(A1-72)+(S13-2);(A1-72)+(S13-3);(A1-72)+(S13-8);
(A1-72)+(S14-1);(A1-72)+(S14-2);(A1-72)+(S14-3);(A1-73)+(S1-1);
(A1-73)+(S1-7);(A1-73)+(S1-11);(A1-73)+(S2-1);(A1-73)+(S3-1);
(A1-73)+(S3-2);(A1-73)+(S3-4);(A1-73)+(S3-7);(A1-73)+(S3-8);
(A1-73)+(S3-10);(A1-73)+(S3-11);(A1-73)+(S4-1);(A1-73)+(S4-5);
(A1-73)+(S4-6);(A1-73)+(S11-1);(A1-73)+(S11-2);(A1-73)+(S11-3);
(A1-73)+(S13-1);(A1-73)+(S13-2);(A1-73)+(S13-3);(A1-73)+(S13-8);
(A1-73)+(S14-1);(A1-73)+(S14-2);(A1-73)+(S14-3);(A1-74)+(S1-1);
(A1-74)+(S1-7);(A1-74)+(S1-11);(A1-74)+(S2-1);(A1-74)+(S3-1);
(A1-74)+(S3-2);(A1-74)+(S3-4);(A1-74)+(S3-7);(A1-74)+(S3-8);
(A1-74)+(S3-10);(A1-74)+(S3-11);(A1-74)+(S4-1);(A1-74)+(S4-5);
(A1-74)+(S4-6);(A1-74)+(S11-1);(A1-74)+(S11-2);(A1-74)+(S11-3);
(A1-74)+(S13-1);(A1-74)+(S13-2);(A1-74)+(S13-3);(A1-74)+(S13-8);
(A1-74)+(S14-1);(A1-74)+(S14-2);(A1-74)+(S14-3);(A1-75)+(S1-1);
(A1-75)+(S1-7);(A1-75)+(S1-11);(A1-75)+(S2-1);(A1-75)+(S3-1);
(A1-75)+(S3-2);(A1-75)+(S3-4);(A1-75)+(S3-7);(A1-75)+(S3-8);
(A1-75)+(S3-10);(A1-75)+(S3-11);(A1-75)+(S4-1);(A1-75)+(S4-5);
(A1-75)+(S4-6);(A1-75)+(S11-1);(A1-75)+(S11-2);(A1-75)+(S11-3);
(A1-75)+(S13-1);(A1-75)+(S13-2);(A1-75)+(S13-3);(A1-75)+(S13-8);
(A1-75)+(S14-1);(A1-75)+(S14-2);(A1-75)+(S14-3);(A1-76)+(S1-1);
(A1-76)+(S1-7);(A1-76)+(S1-11);(A1-76)+(S2-1);(A1-76)+(S3-1);
(A1-76)+(S3-2);(A1-76)+(S3-4);(A1-76)+(S3-7);(A1-76)+(S3-8);
(A1-76)+(S3-10);(A1-76)+(S3-11);(A1-76)+(S4-1);(A1-76)+(S4-5);
(A1-76)+(S4-6);(A1-76)+(S11-1);(A1-76)+(S11-2);(A1-76)+(S11-3);
(A1-76)+(S13-1);(A1-76)+(S13-2);(A1-76)+(S13-3);(A1-76)+(S13-8);
(A1-76)+(S14-1);(A1-76)+(S14-2);(A1-76)+(S14-3);(A1-77)+(S1-1);
(A1-77)+(S1-7);(A1-77)+(S1-11);(A1-77)+(S2-1);(A1-77)+(S3-1);
(A1-77)+(S3-2);(A1-77)+(S3-4);(A1-77)+(S3-7);(A1-77)+(S3-8);
(A1-77)+(S3-10);(A1-77)+(S3-11);(A1-77)+(S4-1);(A1-77)+(S4-5);
(A1-77)+(S4-6);(A1-77)+(S11-1);(A1-77)+(S11-2);(A1-77)+(S11-3);
(A1-77)+(S13-1);(A1-77)+(S13-2);(A1-77)+(S13-3);(A1-77)+(S13-8);
(A1-77)+(S14-1);(A1-77)+(S14-2);(A1-77)+(S14-3);(A1-78)+(S1-1);
(A1-78)+(S1-7);(A1-78)+(S1-11);(A1-78)+(S2-1);(A1-78)+(S3-1);
(A1-78)+(S3-2);(A1-78)+(S3-4);(A1-78)+(S3-7);(A1-78)+(S3-8);
(A1-78)+(S3-10);(A1-78)+(S3-11);(A1-78)+(S4-1);(A1-78)+(S4-5);
(A1-78)+(S4-6);(A1-78)+(S11-1);(A1-78)+(S11-2);(A1-78)+(S11-3);
(A1-78)+(S13-1);(A1-78)+(S13-2);(A1-78)+(S13-3);(A1-78)+(S13-8);
(A1-78)+(S14-1);(A1-78)+(S14-2);(A1-78)+(S14-3);(A1-79)+(S1-1);
(A1-79)+(S1-7);(A1-79)+(S1-11);(A1-79)+(S2-1);(A1-79)+(S3-1);
(A1-79)+(S3-2);(A1-79)+(S3-4);(A1-79)+(S3-7);(A1-79)+(S3-8);
(A1-79)+(S3-10);(A1-79)+(S3-11);(A1-79)+(S4-1);(A1-79)+(S4-5);
(A1-79)+(S4-6);(A1-79)+(S11-1);(A1-79)+(S11-2);(A1-79)+(S11-3);
(A1-79)+(S13-1);(A1-79)+(S13-2);(A1-79)+(S13-3);(A1-79)+(S13-8);
(A1-79)+(S14-1);(A1-79)+(S14-2);(A1-79)+(S14-3);(A1-80)+(S1-1);
(A1-80)+(S1-7);(A1-80)+(S1-11);(A1-80)+(S2-1);(A1-80)+(S3-1);
(A1-80)+(S3-2);(A1-80)+(S3-4);(A1-80)+(S3-7);(A1-80)+(S3-8);
(A1-80)+(S3-10);(A1-80)+(S3-11);(A1-80)+(S4-1);(A1-80)+(S4-5);
(A1-80)+(S4-6);(A1-80)+(S11-1);(A1-80)+(S11-2);(A1-80)+(S11-3);
(A1-80)+(S13-1);(A1-80)+(S13-2);(A1-80)+(S13-3);(A1-80)+(S13-8);
(A1-80)+(S14-1);(A1-80)+(S14-2);(A1-80)+(S14-3);(A1-81)+(S1-1);
(A1-81)+(S1-7);(A1-81)+(S1-11);(A1-81)+(S2-1);(A1-81)+(S3-1);
(A1-81)+(S3-2);(A1-81)+(S3-4);(A1-81)+(S3-7);(A1-81)+(S3-8);
(A1-81)+(S3-10);(A1-81)+(S3-11);(A1-81)+(S4-1);(A1-81)+(S4-5);
(A1-81)+(S4-6);(A1-81)+(S11-1);(A1-81)+(S11-2);(A1-81)+(S11-3);
(A1-81)+(S13-1);(A1-81)+(S13-2);(A1-81)+(S13-3);(A1-81)+(S13-8);
(A1-81)+(S14-1);(A1-81)+(S14-2);(A1-81)+(S14-3);(A1-82)+(S1-1);
(A1-82)+(S1-7);(A1-82)+(S1-11);(A1-82)+(S2-1);(A1-82)+(S3-1);
(A1-82)+(S3-2);(A1-82)+(S3-4);(A1-82)+(S3-7);(A1-82)+(S3-8);
(A1-82)+(S3-10);(A1-82)+(S3-11);(A1-82)+(S4-1);(A1-82)+(S4-5);
(A1-82)+(S4-6);(A1-82)+(S11-1);(A1-82)+(S11-2);(A1-82)+(S11-3);
(A1-82)+(S13-1);(A1-82)+(S13-2);(A1-82)+(S13-3);(A1-82)+(S13-8);
(A1-82)+(S14-1);(A1-82)+(S14-2);(A1-82)+(S14-3);(A1-83)+(S1-1);
(A1-83)+(S1-7);(A1-83)+(S1-11);(A1-83)+(S2-1);(A1-83)+(S3-1);
(A1-83)+(S3-2);(A1-83)+(S3-4);(A1-83)+(S3-7);(A1-83)+(S3-8);
(A1-83)+(S3-10);(A1-83)+(S3-11);(A1-83)+(S4-1);(A1-83)+(S4-5);
(A1-83)+(S4-6);(A1-83)+(S11-1);(A1-83)+(S11-2);(A1-83)+(S11-3);
(A1-83)+(S13-1);(A1-83)+(S13-2);(A1-83)+(S13-3);(A1-83)+(S13-8);
(A1-83)+(S14-1);(A1-83)+(S14-2);(A1-83)+(S14-3);(A1-84)+(S1-1);
(A1-84)+(S1-7);(A1-84)+(S1-11);(A1-84)+(S2-1);(A1-84)+(S3-1);
(A1-84)+(S3-2);(A1-84)+(S3-4);(A1-84)+(S3-7);(A1-84)+(S3-8);
(A1-84)+(S3-10);(A1-84)+(S3-11);(A1-84)+(S4-1);(A1-84)+(S4-5);
(A1-84)+(S4-6);(A1-84)+(S11-1);(A1-84)+(S11-2);(A1-84)+(S11-3);
(A1-84)+(S13-1);(A1-84)+(S13-2);(A1-84)+(S13-3);(A1-84)+(S13-8);
(A1-84)+(S14-1);(A1-84)+(S14-2);(A1-84)+(S14-3);(A1-85)+(S1-1);
(A1-85)+(S1-7);(A1-85)+(S1-11);(A1-85)+(S2-1);(A1-85)+(S3-1);
(A1-85)+(S3-2);(A1-85)+(S3-4);(A1-85)+(S3-7);(A1-85)+(S3-8);
(A1-85)+(S3-10);(A1-85)+(S3-11);(A1-85)+(S4-1);(A1-85)+(S4-5);
(A1-85)+(S4-6);(A1-85)+(S11-1);(A1-85)+(S11-2);(A1-85)+(S11-3);
(A1-85)+(S13-1);(A1-85)+(S13-2);(A1-85)+(S13-3);(A1-85)+(S13-8);
(A1-85)+(S14-1);(A1-85)+(S14-2);(A1-85)+(S14-3);(A1-86)+(S1-1);
(A1-86)+(S1-7);(A1-86)+(S1-11);(A1-86)+(S2-1);(A1-86)+(S3-1);
(A1-86)+(S3-2);(A1-86)+(S3-4);(A1-86)+(S3-7);(A1-86)+(S3-8);
(A1-86)+(S3-10);(A1-86)+(S3-11);(A1-86)+(S4-1);(A1-86)+(S4-5);
(A1-86)+(S4-6);(A1-86)+(S11-1);(A1-86)+(S11-2);(A1-86)+(S11-3);
(A1-86)+(S13-1);(A1-86)+(S13-2);(A1-86)+(S13-3);(A1-86)+(S13-8);
(A1-86)+(S14-1);(A1-86)+(S14-2);(A1-86)+(S14-3);(A1-87)+(S1-1);
(A1-87)+(S1-7);(A1-87)+(S1-11);(A1-87)+(S2-1);(A1-87)+(S3-1);
(A1-87)+(S3-2);(A1-87)+(S3-4);(A1-87)+(S3-7);(A1-87)+(S3-8);
(A1-87)+(S3-10);(A1-87)+(S3-11);(A1-87)+(S4-1);(A1-87)+(S4-5);
(A1-87)+(S4-6);(A1-87)+(S11-1);(A1-87)+(S11-2);(A1-87)+(S11-3);
(A1-87)+(S13-1);(A1-87)+(S13-2);(A1-87)+(S13-3);(A1-87)+(S13-8);
(A1-87)+(S14-1);(A1-87)+(S14-2);(A1-87)+(S14-3);(A1-88)+(S1-1);
(A1-88)+(S1-7);(A1-88)+(S1-11);(A1-88)+(S2-1);(A1-88)+(S3-1);
(A1-88)+(S3-2);(A1-88)+(S3-4);(A1-88)+(S3-7);(A1-88)+(S3-8);
(A1-88)+(S3-10);(A1-88)+(S3-11);(A1-88)+(S4-1);(A1-88)+(S4-5);
(A1-88)+(S4-6);(A1-88)+(S11-1);(A1-88)+(S11-2);(A1-88)+(S11-3);
(A1-88)+(S13-1);(A1-88)+(S13-2);(A1-88)+(S13-3);(A1-88)+(S13-8);
(A1-88)+(S14-1);(A1-88)+(S14-2);(A1-88)+(S14-3);(A1-89)+(S1-1);
(A1-89)+(S1-7);(A1-89)+(S1-11);(A1-89)+(S2-1);(A1-89)+(S3-1);
(A1-89)+(S3-2);(A1-89)+(S3-4);(A1-89)+(S3-7);(A1-89)+(S3-8);
(A1-89)+(S3-10);(A1-89)+(S3-11);(A1-89)+(S4-1);(A1-89)+(S4-5);
(A1-89)+(S4-6);(A1-89)+(S11-1);(A1-89)+(S11-2);(A1-89)+(S11-3);
(A1-89)+(S13-1);(A1-89)+(S13-2);(A1-89)+(S13-3);(A1-89)+(S13-8);
(A1-89)+(S14-1);(A1-89)+(S14-2);(A1-89)+(S14-3);(A1-90)+(S1-1);
(A1-90)+(S1-7);(A1-90)+(S1-11);(A1-90)+(S2-1);(A1-90)+(S3-1);
(A1-90)+(S3-2);(A1-90)+(S3-4);(A1-90)+(S3-7);(A1-90)+(S3-8);
(A1-90)+(S3-10);(A1-90)+(S3-11);(A1-90)+(S4-1);(A1-90)+(S4-5);
(A1-90)+(S4-6);(A1-90)+(S11-1);(A1-90)+(S11-2);(A1-90)+(S11-3);
(A1-90)+(S13-1);(A1-90)+(S13-2);(A1-90)+(S13-3);(A1-90)+(S13-8);
(A1-90)+(S14-1);(A1-90)+(S14-2);(A1-90)+(S14-3);(A1-91)+(S1-1);
(A1-91)+(S1-7);(A1-91)+(S1-11);(A1-91)+(S2-1);(A1-91)+(S3-1);
(A1-91)+(S3-2);(A1-91)+(S3-4);(A1-91)+(S3-7);(A1-91)+(S3-8);
(A1-91)+(S3-10);(A1-91)+(S3-11);(A1-91)+(S4-1);(A1-91)+(S4-5);
(A1-91)+(S4-6);(A1-91)+(S11-1);(A1-91)+(S11-2);(A1-91)+(S11-3);
(A1-91)+(S13-1);(A1-91)+(S13-2);(A1-91)+(S13-3);(A1-91)+(S13-8);
(A1-91)+(S14-1);(A1-91)+(S14-2);(A1-91)+(S14-3);(A1-92)+(S1-1);
(A1-92)+(S1-7);(A1-92)+(S1-11);(A1-92)+(S2-1);(A1-92)+(S3-1);
(A1-92)+(S3-2);(A1-92)+(S3-4);(A1-92)+(S3-7);(A1-92)+(S3-8);
(A1-92)+(S3-10);(A1-92)+(S3-11);(A1-92)+(S4-1);(A1-92)+(S4-5);
(A1-92)+(S4-6);(A1-92)+(S11-1);(A1-92)+(S11-2);(A1-92)+(S11-3);
(A1-92)+(S13-1);(A1-92)+(S13-2);(A1-92)+(S13-3);(A1-92)+(S13-8);
(A1-92)+(S14-1);(A1-92)+(S14-2);(A1-92)+(S14-3);(A1-93)+(S1-1);
(A1-93)+(S1-7);(A1-93)+(S1-11);(A1-93)+(S2-1);(A1-93)+(S3-1);
(A1-93)+(S3-2);(A1-93)+(S3-4);(A1-93)+(S3-7);(A1-93)+(S3-8);
(A1-93)+(S3-10);(A1-93)+(S3-11);(A1-93)+(S4-1);(A1-93)+(S4-5);
(A1-93)+(S4-6);(A1-93)+(S11-1);(A1-93)+(S11-2);(A1-93)+(S11-3);
(A1-93)+(S13-1);(A1-93)+(S13-2);(A1-93)+(S13-3);(A1-93)+(S13-8);
(A1-93)+(S14-1);(A1-93)+(S14-2);(A1-93)+(S14-3);(A1-94)+(S1-1);
(A1-94)+(S1-7);(A1-94)+(S1-11);(A1-94)+(S2-1);(A1-94)+(S3-1);
(A1-94)+(S3-2);(A1-94)+(S3-4);(A1-94)+(S3-7);(A1-94)+(S3-8);
(A1-94)+(S3-10);(A1-94)+(S3-11);(A1-94)+(S4-1);(A1-94)+(S4-5);
(A1-94)+(S4-6);(A1-94)+(S11-1);(A1-94)+(S11-2);(A1-94)+(S11-3);
(A1-94)+(S13-1);(A1-94)+(S13-2);(A1-94)+(S13-3);(A1-94)+(S13-8);
(A1-94)+(S14-1);(A1-94)+(S14-2);(A1-94)+(S14-3);(A1-95)+(S1-1);
(A1-95)+(S1-7);(A1-95)+(S1-11);(A1-95)+(S2-1);(A1-95)+(S3-1);
(A1-95)+(S3-2);(A1-95)+(S3-4);(A1-95)+(S3-7);(A1-95)+(S3-8);
(A1-95)+(S3-10);(A1-95)+(S3-11);(A1-95)+(S4-1);(A1-95)+(S4-5);
(A1-95)+(S4-6);(A1-95)+(S11-1);(A1-95)+(S11-2);(A1-95)+(S11-3);
(A1-95)+(S13-1);(A1-95)+(S13-2);(A1-95)+(S13-3);(A1-95)+(S13-8);
(A1-95)+(S14-1);(A1-95)+(S14-2);(A1-95)+(S14-3);(A1-96)+(S1-1);
(A1-96)+(S1-7);(A1-96)+(S1-11);(A1-96)+(S2-1);(A1-96)+(S3-1);
(A1-96)+(S3-2);(A1-96)+(S3-4);(A1-96)+(S3-7);(A1-96)+(S3-8);
(A1-96)+(S3-10);(A1-96)+(S3-11);(A1-96)+(S4-1);(A1-96)+(S4-5);
(A1-96)+(S4-6);(A1-96)+(S11-1);(A1-96)+(S11-2);(A1-96)+(S11-3);
(A1-96)+(S13-1);(A1-96)+(S13-2);(A1-96)+(S13-3);(A1-96)+(S13-8);
(A1-96)+(S14-1);(A1-96)+(S14-2);(A1-96)+(S14-3);(A1-97)+(S1-1);
(A1-97)+(S1-7);(A1-97)+(S1-11);(A1-97)+(S2-1);(A1-97)+(S3-1);
(A1-97)+(S3-2);(A1-97)+(S3-4);(A1-97)+(S3-7);(A1-97)+(S3-8);
(A1-97)+(S3-10);(A1-97)+(S3-11);(A1-97)+(S4-1);(A1-97)+(S4-5);
(A1-97)+(S4-6);(A1-97)+(S11-1);(A1-97)+(S11-2);(A1-97)+(S11-3);
(A1-97)+(S13-1);(A1-97)+(S13-2);(A1-97)+(S13-3);(A1-97)+(S13-8);
(A1-97)+(S14-1);(A1-97)+(S14-2);(A1-97)+(S14-3);(A1-98)+(S1-1);
(A1-98)+(S1-7);(A1-98)+(S1-11);(A1-98)+(S2-1);(A1-98)+(S3-1);
(A1-98)+(S3-2);(A1-98)+(S3-4);(A1-98)+(S3-7);(A1-98)+(S3-8);
(A1-98)+(S3-10);(A1-98)+(S3-11);(A1-98)+(S4-1);(A1-98)+(S4-5);
(A1-98)+(S4-6);(A1-98)+(S11-1);(A1-98)+(S11-2);(A1-98)+(S11-3);
(A1-98)+(S13-1);(A1-98)+(S13-2);(A1-98)+(S13-3);(A1-98)+(S13-8);
(A1-98)+(S14-1);(A1-98)+(S14-2);(A1-98)+(S14-3);(A1-99)+(S1-1);
(A1-99)+(S1-7);(A1-99)+(S1-11);(A1-99)+(S2-1);(A1-99)+(S3-1);
(A1-99)+(S3-2);(A1-99)+(S3-4);(A1-99)+(S3-7);(A1-99)+(S3-8);
(A1-99)+(S3-10);(A1-99)+(S3-11);(A1-99)+(S4-1);(A1-99)+(S4-5);
(A1-99)+(S4-6);(A1-99)+(S11-1);(A1-99)+(S11-2);(A1-99)+(S11-3);
(A1-99)+(S13-1);(A1-99)+(S13-2);(A1-99)+(S13-3);(A1-99)+(S13-8);
(A1-99)+(S14-1);(A1-99)+(S14-2);(A1-99)+(S14-3);(A1-100)+(S1-1);
(A1-100)+(S1-7);(A1-100)+(S1-11);(A1-100)+(S2-1);(A1-100)+(S3-1);
(A1-100)+(S3-2);(A1-100)+(S3-4);(A1-100)+(S3-7);(A1-100)+(S3-8);
(A1-100)+(S3-10);(A1-100)+(S3-11);(A1-100)+(S4-1);(A1-100)+(S4-5);
(A1-100)+(S4-6);(A1-100)+(S11-1);(A1-100)+(S11-2);(A1-100)+(S11-3);
(A1-100)+(S13-1);(A1-100)+(S13-2);(A1-100)+(S13-3);(A1-100)+(S13-8);
(A1-100)+(S14-1);(A1-100)+(S14-2);(A1-100)+(S14-3);(A1-101)+(S1-1);
(A1-101)+(S1-7);(A1-101)+(S1-11);(A1-101)+(S2-1);(A1-101)+(S3-1);
(A1-101)+(S3-2);(A1-101)+(S3-4);(A1-101)+(S3-7);(A1-101)+(S3-8);
(A1-101)+(S3-10);(A1-101)+(S3-11);(A1-101)+(S4-1);(A1-101)+(S4-5);
(A1-101)+(S4-6);(A1-101)+(S11-1);(A1-101)+(S11-2);(A1-101)+(S11-3);
(A1-101)+(S13-1);(A1-101)+(S13-2);(A1-101)+(S13-3);(A1-101)+(S13-8);
(A1-101)+(S14-1);(A1-101)+(S14-2);(A1-101)+(S14-3);(A1-102)+(S1-1);
(A1-102)+(S1-7);(A1-102)+(S1-11);(A1-102)+(S2-1);(A1-102)+(S3-1);
(A1-102)+(S3-2);(A1-102)+(S3-4);(A1-102)+(S3-7);(A1-102)+(S3-8);
(A1-102)+(S3-10);(A1-102)+(S3-11);(A1-102)+(S4-1);(A1-102)+(S4-5);
(A1-102)+(S4-6);(A1-102)+(S11-1);(A1-102)+(S11-2);(A1-102)+(S11-3);
(A1-102)+(S13-1);(A1-102)+(S13-2);(A1-102)+(S13-3);(A1-102)+(S13-8);
(A1-102)+(S14-1);(A1-102)+(S14-2);(A1-102)+(S14-3);(A1-103)+(S1-1);
(A1-103)+(S1-7);(A1-103)+(S1-11);(A1-103)+(S2-1);(A1-103)+(S3-1);
(A1-103)+(S3-2);(A1-103)+(S3-4);(A1-103)+(S3-7);(A1-103)+(S3-8);
(A1-103)+(S3-10);(A1-103)+(S3-11);(A1-103)+(S4-1);(A1-103)+(S4-5);
(A1-103)+(S4-6);(A1-103)+(S11-1);(A1-103)+(S11-2);(A1-103)+(S11-3);
(A1-103)+(S13-1);(A1-103)+(S13-2);(A1-103)+(S13-3);(A1-103)+(S13-8);
(A1-103)+(S14-1);(A1-103)+(S14-2);(A1-103)+(S14-3);(A1-104)+(S1-1);
(A1-104)+(S1-7);(A1-104)+(S1-11);(A1-104)+(S2-1);(A1-104)+(S3-1);
(A1-104)+(S3-2);(A1-104)+(S3-4);(A1-104)+(S3-7);(A1-104)+(S3-8);
(A1-104)+(S3-10);(A1-104)+(S3-11);(A1-104)+(S4-1);(A1-104)+(S4-5);
(A1-104)+(S4-6);(A1-104)+(S11-1);(A1-104)+(S11-2);(A1-104)+(S11-3);
(A1-104)+(S13-1);(A1-104)+(S13-2);(A1-104)+(S13-3);(A1-104)+(S13-8);
(A1-104)+(S14-1);(A1-104)+(S14-2);(A1-104)+(S14-3);(A1-105)+(S1-1);
(A1-105)+(S1-7);(A1-105)+(S1-11);(A1-105)+(S2-1);(A1-105)+(S3-1);
(A1-105)+(S3-2);(A1-105)+(S3-4);(A1-105)+(S3-7);(A1-105)+(S3-8);
(A1-105)+(S3-10);(A1-105)+(S3-11);(A1-105)+(S4-1);(A1-105)+(S4-5);
(A1-105)+(S4-6);(A1-105)+(S11-1);(A1-105)+(S11-2);(A1-105)+(S11-3);
(A1-105)+(S13-1);(A1-105)+(S13-2);(A1-105)+(S13-3);(A1-105)+(S13-8);
(A1-105)+(S14-1);(A1-105)+(S14-2);(A1-105)+(S14-3);(A1-106)+(S1-1);
(A1-106)+(S1-7);(A1-106)+(S1-11);(A1-106)+(S2-1);(A1-106)+(S3-1);
(A1-106)+(S3-2);(A1-106)+(S3-4);(A1-106)+(S3-7);(A1-106)+(S3-8);
(A1-106)+(S3-10);(A1-106)+(S3-11);(A1-106)+(S4-1);(A1-106)+(S4-5);
(A1-106)+(S4-6);(A1-106)+(S11-1);(A1-106)+(S11-2);(A1-106)+(S11-3);
(A1-106)+(S13-1);(A1-106)+(S13-2);(A1-106)+(S13-3);(A1-106)+(S13-8);
(A1-106)+(S14-1);(A1-106)+(S14-2);(A1-106)+(S14-3);(A2-1)+(S1-1);
(A2-1)+(S1-7);(A2-1)+(S1-11);(A2-1)+(S2-1);(A2-1)+(S3-1);
(A2-1)+(S3-2);(A2-1)+(S3-4);(A2-1)+(S3-7);(A2-1)+(S3-8);
(A2-1)+(S3-10);(A2-1)+(S3-11);(A2-1)+(S4-1);(A2-1)+(S4-5);
(A2-1)+(S4-6);(A2-1)+(S11-1);(A2-1)+(S11-2);(A2-1)+(S11-3);
(A2-1)+(S13-1);(A2-1)+(S13-2);(A2-1)+(S13-3);(A2-1)+(S13-8);
(A2-1)+(S14-1);(A2-1)+(S14-2);(A2-1)+(S14-3);(A2-2)+(S1-1);
(A2-2)+(S1-7);(A2-2)+(S1-11);(A2-2)+(S2-1);(A2-2)+(S3-1);
(A2-2)+(S3-2);(A2-2)+(S3-4);(A2-2)+(S3-7);(A2-2)+(S3-8);
(A2-2)+(S3-10);(A2-2)+(S3-11);(A2-2)+(S4-1);(A2-2)+(S4-5);
(A2-2)+(S4-6);(A2-2)+(S11-1);(A2-2)+(S11-2);(A2-2)+(S11-3);
(A2-2)+(S13-1);(A2-2)+(S13-2);(A2-2)+(S13-3);(A2-2)+(S13-8);
(A2-2)+(S14-1);(A2-2)+(S14-2);(A2-2)+(S14-3);(A2-3)+(S1-1);
(A2-3)+(S1-7);(A2-3)+(S1-11);(A2-3)+(S2-1);(A2-3)+(S3-1);
(A2-3)+(S3-2);(A2-3)+(S3-4);(A2-3)+(S3-7);(A2-3)+(S3-8);
(A2-3)+(S3-10);(A2-3)+(S3-11);(A2-3)+(S4-1);(A2-3)+(S4-5);
(A2-3)+(S4-6);(A2-3)+(S11-1);(A2-3)+(S11-2);(A2-3)+(S11-3);
(A2-3)+(S13-1);(A2-3)+(S13-2);(A2-3)+(S13-3);(A2-3)+(S13-8);
(A2-3)+(S14-1);(A2-3)+(S14-2);(A2-3)+(S14-3);(A2-4)+(S1-1);
(A2-4)+(S1-7);(A2-4)+(S1-11);(A2-4)+(S2-1);(A2-4)+(S3-1);
(A2-4)+(S3-2);(A2-4)+(S3-4);(A2-4)+(S3-7);(A2-4)+(S3-8);
(A2-4)+(S3-10);(A2-4)+(S3-11);(A2-4)+(S4-1);(A2-4)+(S4-5);
(A2-4)+(S4-6);(A2-4)+(S11-1);(A2-4)+(S11-2);(A2-4)+(S11-3);
(A2-4)+(S13-1);(A2-4)+(S13-2);(A2-4)+(S13-3);(A2-4)+(S13-8);
(A2-4)+(S14-1);(A2-4)+(S14-2);(A2-4)+(S14-3);(A2-5)+(S1-1);
(A2-5)+(S1-7);(A2-5)+(S1-11);(A2-5)+(S2-1);(A2-5)+(S3-1);
(A2-5)+(S3-2);(A2-5)+(S3-4);(A2-5)+(S3-7);(A2-5)+(S3-8);
(A2-5)+(S3-10);(A2-5)+(S3-11);(A2-5)+(S4-1);(A2-5)+(S4-5);
(A2-5)+(S4-6);(A2-5)+(S11-1);(A2-5)+(S11-2);(A2-5)+(S11-3);
(A2-5)+(S13-1);(A2-5)+(S13-2);(A2-5)+(S13-3);(A2-5)+(S13-8);
(A2-5)+(S14-1);(A2-5)+(S14-2);(A2-5)+(S14-3);(A2-6)+(S1-1);
(A2-6)+(S1-7);(A2-6)+(S1-11);(A2-6)+(S2-1);(A2-6)+(S3-1);
(A2-6)+(S3-2);(A2-6)+(S3-4);(A2-6)+(S3-7);(A2-6)+(S3-8);
(A2-6)+(S3-10);(A2-6)+(S3-11);(A2-6)+(S4-1);(A2-6)+(S4-5);
(A2-6)+(S4-6);(A2-6)+(S11-1);(A2-6)+(S11-2);(A2-6)+(S11-3);
(A2-6)+(S13-1);(A2-6)+(S13-2);(A2-6)+(S13-3);(A2-6)+(S13-8);
(A2-6)+(S14-1);(A2-6)+(S14-2);(A2-6)+(S14-3);(A2-7)+(S1-1);
(A2-7)+(S1-7);(A2-7)+(S1-11);(A2-7)+(S2-1);(A2-7)+(S3-1);
(A2-7)+(S3-2);(A2-7)+(S3-4);(A2-7)+(S3-7);(A2-7)+(S3-8);
(A2-7)+(S3-10);(A2-7)+(S3-11);(A2-7)+(S4-1);(A2-7)+(S4-5);
(A2-7)+(S4-6);(A2-7)+(S11-1);(A2-7)+(S11-2);(A2-7)+(S11-3);
(A2-7)+(S13-1);(A2-7)+(S13-2);(A2-7)+(S13-3);(A2-7)+(S13-8);
(A2-7)+(S14-1);(A2-7)+(S14-2);(A2-7)+(S14-3);(A2-8)+(S1-1);
(A2-8)+(S1-7);(A2-8)+(S1-11);(A2-8)+(S2-1);(A2-8)+(S3-1);
(A2-8)+(S3-2);(A2-8)+(S3-4);(A2-8)+(S3-7);(A2-8)+(S3-8);
(A2-8)+(S3-10);(A2-8)+(S3-11);(A2-8)+(S4-1);(A2-8)+(S4-5);
(A2-8)+(S4-6);(A2-8)+(S11-1);(A2-8)+(S11-2);(A2-8)+(S11-3);
(A2-8)+(S13-1);(A2-8)+(S13-2);(A2-8)+(S13-3);(A2-8)+(S13-8);
(A2-8)+(S14-1);(A2-8)+(S14-2);(A2-8)+(S14-3);(A2-9)+(S1-1);
(A2-9)+(S1-7);(A2-9)+(S1-11);(A2-9)+(S2-1);(A2-9)+(S3-1);
(A2-9)+(S3-2);(A2-9)+(S3-4);(A2-9)+(S3-7);(A2-9)+(S3-8);
(A2-9)+(S3-10);(A2-9)+(S3-11);(A2-9)+(S4-1);(A2-9)+(S4-5);
(A2-9)+(S4-6);(A2-9)+(S11-1);(A2-9)+(S11-2);(A2-9)+(S11-3);
(A2-9)+(S13-1);(A2-9)+(S13-2);(A2-9)+(S13-3);(A2-9)+(S13-8);
(A2-9)+(S14-1);(A2-9)+(S14-2);(A2-9)+(S14-3);(A2-10)+(S1-1);
(A2-10)+(S1-7);(A2-10)+(S1-11);(A2-10)+(S2-1);(A2-10)+(S3-1);
(A2-10)+(S3-2);(A2-10)+(S3-4);(A2-10)+(S3-7);(A2-10)+(S3-8);
(A2-10)+(S3-10);(A2-10)+(S3-11);(A2-10)+(S4-1);(A2-10)+(S4-5);
(A2-10)+(S4-6);(A2-10)+(S11-1);(A2-10)+(S11-2);(A2-10)+(S11-3);
(A2-10)+(S13-1);(A2-10)+(S13-2);(A2-10)+(S13-3);(A2-10)+(S13-8);
(A2-10)+(S14-1);(A2-10)+(S14-2);(A2-10)+(S14-3);(A2-11)+(S1-1);
(A2-11)+(S1-7);(A2-11)+(S1-11);(A2-11)+(S2-1);(A2-11)+(S3-1);
(A2-11)+(S3-2);(A2-11)+(S3-4);(A2-11)+(S3-7);(A2-11)+(S3-8);
(A2-11)+(S3-10);(A2-11)+(S3-11);(A2-11)+(S4-1);(A2-11)+(S4-5);
(A2-11)+(S4-6);(A2-11)+(S11-1);(A2-11)+(S11-2);(A2-11)+(S11-3);
(A2-11)+(S13-1);(A2-11)+(S13-2);(A2-11)+(S13-3);(A2-11)+(S13-8);
(A2-11)+(S14-1);(A2-11)+(S14-2);(A2-11)+(S14-3);(A2-12)+(S1-1);
(A2-12)+(S1-7);(A2-12)+(S1-11);(A2-12)+(S2-1);(A2-12)+(S3-1);
(A2-12)+(S3-2);(A2-12)+(S3-4);(A2-12)+(S3-7);(A2-12)+(S3-8);
(A2-12)+(S3-10);(A2-12)+(S3-11);(A2-12)+(S4-1);(A2-12)+(S4-5);
(A2-12)+(S4-6);(A2-12)+(S11-1);(A2-12)+(S11-2);(A2-12)+(S11-3);
(A2-12)+(S13-1);(A2-12)+(S13-2);(A2-12)+(S13-3);(A2-12)+(S13-8);
(A2-12)+(S14-1);(A2-12)+(S14-2);(A2-12)+(S14-3);(A2-13)+(S1-1);
(A2-13)+(S1-7);(A2-13)+(S1-11);(A2-13)+(S2-1);(A2-13)+(S3-1);
(A2-13)+(S3-2);(A2-13)+(S3-4);(A2-13)+(S3-7);(A2-13)+(S3-8);
(A2-13)+(S3-10);(A2-13)+(S3-11);(A2-13)+(S4-1);(A2-13)+(S4-5);
(A2-13)+(S4-6);(A2-13)+(S11-1);(A2-13)+(S11-2);(A2-13)+(S11-3);
(A2-13)+(S13-1);(A2-13)+(S13-2);(A2-13)+(S13-3);(A2-13)+(S13-8);
(A2-13)+(S14-1);(A2-13)+(S14-2);(A2-13)+(S14-3);(A2-14)+(S1-1);
(A2-14)+(S1-7);(A2-14)+(S1-11);(A2-14)+(S2-1);(A2-14)+(S3-1);
(A2-14)+(S3-2);(A2-14)+(S3-4);(A2-14)+(S3-7);(A2-14)+(S3-8);
(A2-14)+(S3-10);(A2-14)+(S3-11);(A2-14)+(S4-1);(A2-14)+(S4-5);
(A2-14)+(S4-6);(A2-14)+(S11-1);(A2-14)+(S11-2);(A2-14)+(S11-3);
(A2-14)+(S13-1);(A2-14)+(S13-2);(A2-14)+(S13-3);(A2-14)+(S13-8);
(A2-14)+(S14-1);(A2-14)+(S14-2);(A2-14)+(S14-3);(A2-15)+(S1-1);
(A2-15)+(S1-7);(A2-15)+(S1-11);(A2-15)+(S2-1);(A2-15)+(S3-1);
(A2-15)+(S3-2);(A2-15)+(S3-4);(A2-15)+(S3-7);(A2-15)+(S3-8);
(A2-15)+(S3-10);(A2-15)+(S3-11);(A2-15)+(S4-1);(A2-15)+(S4-5);
(A2-15)+(S4-6);(A2-15)+(S11-1);(A2-15)+(S11-2);(A2-15)+(S11-3);
(A2-15)+(S13-1);(A2-15)+(S13-2);(A2-15)+(S13-3);(A2-15)+(S13-8);
(A2-15)+(S14-1);(A2-15)+(S14-2);(A2-15)+(S14-3);(A2-16)+(S1-1);
(A2-16)+(S1-7);(A2-16)+(S1-11);(A2-16)+(S2-1);(A2-16)+(S3-1);
(A2-16)+(S3-2);(A2-16)+(S3-4);(A2-16)+(S3-7);(A2-16)+(S3-8);
(A2-16)+(S3-10);(A2-16)+(S3-11);(A2-16)+(S4-1);(A2-16)+(S4-5);
(A2-16)+(S4-6);(A2-16)+(S11-1);(A2-16)+(S11-2);(A2-16)+(S11-3);
(A2-16)+(S13-1);(A2-16)+(S13-2);(A2-16)+(S13-3);(A2-16)+(S13-8);
(A2-16)+(S14-1);(A2-16)+(S14-2);(A2-16)+(S14-3);(A2-17)+(S1-1);
(A2-17)+(S1-7);(A2-17)+(S1-11);(A2-17)+(S2-1);(A2-17)+(S3-1);
(A2-17)+(S3-2);(A2-17)+(S3-4);(A2-17)+(S3-7);(A2-17)+(S3-8);
(A2-17)+(S3-10);(A2-17)+(S3-11);(A2-17)+(S4-1);(A2-17)+(S4-5);
(A2-17)+(S4-6);(A2-17)+(S11-1);(A2-17)+(S11-2);(A2-17)+(S11-3);
(A2-17)+(S13-1);(A2-17)+(S13-2);(A2-17)+(S13-3);(A2-17)+(S13-8);
(A2-17)+(S14-1);(A2-17)+(S14-2);(A2-17)+(S14-3);(A2-18)+(S1-1);
(A2-18)+(S1-7);(A2-18)+(S1-11);(A2-18)+(S2-1);(A2-18)+(S3-1);
(A2-18)+(S3-2);(A2-18)+(S3-4);(A2-18)+(S3-7);(A2-18)+(S3-8);
(A2-18)+(S3-10);(A2-18)+(S3-11);(A2-18)+(S4-1);(A2-18)+(S4-5);
(A2-18)+(S4-6);(A2-18)+(S11-1);(A2-18)+(S11-2);(A2-18)+(S11-3);
(A2-18)+(S13-1);(A2-18)+(S13-2);(A2-18)+(S13-3);(A2-18)+(S13-8);
(A2-18)+(S14-1);(A2-18)+(S14-2);(A2-18)+(S14-3);(A2-19)+(S1-1);
(A2-19)+(S1-7);(A2-19)+(S1-11);(A2-19)+(S2-1);(A2-19)+(S3-1);
(A2-19)+(S3-2);(A2-19)+(S3-4);(A2-19)+(S3-7);(A2-19)+(S3-8);
(A2-19)+(S3-10);(A2-19)+(S3-11);(A2-19)+(S4-1);(A2-19)+(S4-5);
(A2-19)+(S4-6);(A2-19)+(S11-1);(A2-19)+(S11-2);(A2-19)+(S11-3);
(A2-19)+(S13-1);(A2-19)+(S13-2);(A2-19)+(S13-3);(A2-19)+(S13-8);
(A2-19)+(S14-1);(A2-19)+(S14-2);(A2-19)+(S14-3);(A2-20)+(S1-1);
(A2-20)+(S1-7);(A2-20)+(S1-11);(A2-20)+(S2—1);(A2-20)+(S3-1);
(A2-20)+(S3-2);(A2-20)+(S3-4);(A2-20)+(S3—7);(A2-20)+(S3-8);
(A2-20)+(S3-10);(A2-20)+(S3-11);(A2-20)+(S4-1);(A2-20)+(S4-5);
(A2-20)+(S4-6);(A2-20)+(S11-1);(A2-20)+(S11-2);(A2-20)+(S11-3);
(A2-20)+(S13-1);(A2-20)+(S13-2);(A2-20)+(S13-3);(A2-20)+(S13-8);
(A2-20)+(S14-1);(A2-20)+(S14-2);(A2-20)+(S14-3);(A2-21)+(S1-1);
(A2-21)+(S1-7);(A2-21)+(S1-11);(A2-21)+(S2-1);(A2-21)+(S3-1);
(A2-21)+(S3-2);(A2-21)+(S3-4);(A2-21)+(S3-7);(A2-21)+(S3-8);
(A2-21)+(S3-10);(A2-21)+(S3-11);(A2-21)+(S4-1);(A2-21)+(S4-5);
(A2-21)+(S4-6);(A2-21)+(S11-1);(A2-21)+(S11-2);(A2-21)+(S11-3);
(A2-21)+(S13-1);(A2-21)+(S13-2);(A2-21)+(S13-3);(A2-21)+(S13-8);
(A2-21)+(S14-1);(A2-21)+(S14-2);(A2-21)+(S14-3);(A2-22)+(S1-1);
(A2-22)+(S1-7);(A2-22)+(S1-11);(A2-22)+(S2-1);(A2-22)+(S3-1);
(A2-22)+(S3-2);(A2-22)+(S3-4);(A2-22)+(S3-7);(A2-22)+(S3-8);
(A2-22)+(S3-10);(A2-22)+(S3-11);(A2-22)+(S4-1);(A2-22)+(S4-5);
(A2-22)+(S4-6);(A2-22)+(S11-1);(A2-22)+(S11-2);(A2-22)+(S11-3);
(A2-22)+(S13-1);(A2-22)+(S13-2);(A2-22)+(S13-3);(A2-22)+(S13-8);
(A2-22)+(S14-1);(A2-22)+(S14-2);(A2-22)+(S14-3);(A2-23)+(S1-1);
(A2-23)+(S1-7);(A2-23)+(S1-11);(A2-23)+(S2-1);(A2-23)+(S3-1);
(A2-23)+(S3-2);(A2-23)+(S3-4);(A2-23)+(S3-7);(A2-23)+(S3-8);
(A2-23)+(S3-10);(A2-23)+(S3-11);(A2-23)+(S4-1);(A2-23)+(S4-5);
(A2-23)+(S4-6);(A2-23)+(S11-1);(A2-23)+(S11-2);(A2-23)+(S11-3);
(A2-23)+(S13-1);(A2-23)+(S13-2);(A2-23)+(S13-3);(A2-23)+(S13-8);
(A2-23)+(S14-1);(A2-23)+(S14-2);(A2-23)+(S14-3);(A2-24)+(S1-1);
(A2-24)+(S1-7);(A2-24)+(S1-11);(A2-24)+(S2-1);(A2-24)+(S3-1);
(A2-24)+(S3-2);(A2-24)+(S3-4);(A2-24)+(S3-7);(A2-24)+(S3-8);
(A2-24)+(S3-10);(A2-24)+(S3-11);(A2-24)+(S4-1);(A2-24)+(S4-5);
(A2-24)+(S4-6);(A2-24)+(S11-1);(A2-24)+(S11-2);(A2-24)+(S11-3);
(A2-24)+(S13-1);(A2-24)+(S13-2);(A2-24)+(S13-3);(A2-24)+(S13-8);
(A2-24)+(S14-1);(A2-24)+(S14-2);(A2-24)+(S14-3);(A2-25)+(S1-1);
(A2-25)+(S1-7);(A2-25)+(S1-11);(A2-25)+(S2-1);(A2-25)+(S3-1);
(A2-25)+(S3-2);(A2-25)+(S3-4);(A2-25)+(S3-7);(A2-25)+(S3-8);
(A2-25)+(S3-10);(A2-25)+(S3-11);(A2-25)+(S4-1);(A2-25)+(S4-5);
(A2-25)+(S4-6);(A2-25)+(S11-1);(A2-25)+(S11-2);(A2-25)+(S11-3);
(A2-25)+(S13-1);(A2-25)+(S13-2);(A2-25)+(S13-3);(A2-25)+(S13-8);
(A2-25)+(S14-1);(A2-25)+(S14-2);(A2-25)+(S14-3);(A2-26)+(S1-1);
(A2-26)+(S1-7);(A2-26)+(S1-11);(A2-26)+(S2-1);(A2-26)+(S3-1);
(A2-26)+(S3-2);(A2-26)+(S3-4);(A2-26)+(S3-7);(A2-26)+(S3-8);
(A2-26)+(S3-10);(A2-26)+(S3-11);(A2-26)+(S4-1);(A2-26)+(S4-5);
(A2-26)+(S4-6);(A2-26)+(S11-1);(A2-26)+(S11-2);(A2-26)+(S11-3);
(A2-26)+(S13-1);(A2-26)+(S13-2);(A2-26)+(S13-3);(A2-26)+(S13-8);
(A2-26)+(S14-1);(A2-26)+(S14-2);(A2-26)+(S14-3);(A2-27)+(S1-1);
(A2-27)+(S1-7);(A2-27)+(S1-11);(A2-27)+(S2-1);(A2-27)+(S3-1);
(A2-27)+(S3-2);(A2-27)+(S3-4);(A2-27)+(S3-7);(A2-27)+(S3-8);
(A2-27)+(S3-10);(A2-27)+(S3-11);(A2-27)+(S4-1);(A2-27)+(S4-5);
(A2-27)+(S4-6);(A2-27)+(S11-1);(A2-27)+(S11-2);(A2-27)+(S11-3);
(A2-27)+(S13-1);(A2-27)+(S13-2);(A2-27)+(S13-3);(A2-27)+(S13-8);
(A2-27)+(S14-1);(A2-27)+(S14-2);(A2-27)+(S14-3);(A2-28)+(S1-1);
(A2-28)+(S1-7);(A2-28)+(S1-11);(A2-28)+(S2-1);(A2-28)+(S3-1);
(A2-28)+(S3-2);(A2-28)+(S3-4);(A2-28)+(S3-7);(A2-28)+(S3-8);
(A2-28)+(S3-10);(A2-28)+(S3-11);(A2-28)+(S4-1);(A2-28)+(S4-5);
(A2-28)+(S4-6);(A2-28)+(S11-1);(A2-28)+(S11-2);(A2-28)+(S11-3);
(A2-28)+(S13-1);(A2-28)+(S13-2);(A2-28)+(S13-3);(A2-28)+(S13-8);
(A2-28)+(S14-1);(A2-28)+(S14-2);(A2-28)+(S14-3);(A2-29)+(S1-1);
(A2-29)+(S1-7);(A2-29)+(S1-11);(A2-29)+(S2-1);(A2-29)+(S3-1);
(A2-29)+(S3-2);(A2-29)+(S3-4);(A2-29)+(S3-7);(A2-29)+(S3-8);
(A2-29)+(S3-10);(A2-29)+(S3-11);(A2-29)+(S4-1);(A2-29)+(S4-5);
(A2-29)+(S4-6);(A2-29)+(S11-1);(A2-29)+(S11-2);(A2-29)+(S11-3);
(A2-29)+(S13-1);(A2-29)+(S13-2);(A2-29)+(S13-3);(A2-29)+(S13-8);
(A2-29)+(S14-1);(A2-29)+(S14-2);(A2-29)+(S14-3);(A2-30)+(S1-1);
(A2-30)+(S1-7);(A2-30)+(S1-11);(A2-30)+(S2-1);(A2-30)+(S3-1);
(A2-30)+(S3-2);(A2-30)+(S3-4);(A2-30)+(S3-7);(A2-30)+(S3-8);
(A2-30)+(S3-10);(A2-30)+(S3-11);(A2-30)+(S4-1);(A2-30)+(S4-5);
(A2-30)+(S4-6);(A2-30)+(S11-1);(A2-30)+(S11-2);(A2-30)+(S11-3);
(A2-30)+(S13-1);(A2-30)+(S13-2);(A2-30)+(S13-3);(A2-30)+(S13-8);
(A2-30)+(S14-1);(A2-30)+(S14-2);(A2-30)+(S14-3);(A2-31)+(S1-1);
(A2-31)+(S1-7);(A2-31)+(S1-11);(A2-31)+(S2-1);(A2-31)+(S3-1);
(A2-31)+(S3-2);(A2-31)+(S3-4);(A2-31)+(S3-7);(A2-31)+(S3-8);
(A2-31)+(S3-10);(A2-31)+(S3-11);(A2-31)+(S4-1);(A2-31)+(S4-5);
(A2-31)+(S4-6);(A2-31)+(S11-1);(A2-31)+(S11-2);(A2-31)+(S11-3);
(A2-31)+(S13-1);(A2-31)+(S13-2);(A2-31)+(S13-3);(A2-31)+(S13-8);
(A2-31)+(S14-1);(A2-31)+(S14-2);(A2-31)+(S14-3);(A2-32)+(S1-1);
(A2-32)+(S1-7);(A2-32)+(S1-11);(A2-32)+(S2-1);(A2-32)+(S3-1);
(A2-32)+(S3-2);(A2-32)+(S3-4);(A2-32)+(S3-7);(A2-32)+(S3-8);
(A2-32)+(S3-10);(A2-32)+(S3-11);(A2-32)+(S4-1);(A2-32)+(S4-5);
(A2-32)+(S4-6);(A2-32)+(S11-1);(A2-32)+(S11-2);(A2-32)+(S11-3);
(A2-32)+(S13-1);(A2-32)+(S13-2);(A2-32)+(S13-3);(A2-32)+(S13-8);
(A2-32)+(S14-1);(A2-32)+(S14-2);(A2-32)+(S14-3);(A2-33)+(S1-1);
(A2-33)+(S1-7);(A2-33)+(S1-11);(A2-33)+(S2-1);(A2-33)+(S3-1);
(A2-33)+(S3-2);(A2-33)+(S3-4);(A2-33)+(S3-7);(A2-33)+(S3-8);
(A2-33)+(S3-10);(A2-33)+(S3-11);(A2-33)+(S4-1);(A2-33)+(S4-5);
(A2-33)+(S4-6);(A2-33)+(S11-1);(A2-33)+(S11-2);(A2-33)+(S11-3);
(A2-33)+(S13-1);(A2-33)+(S13-2);(A2-33)+(S13-3);(A2-33)+(S13-8);
(A2-33)+(S14-1);(A2-33)+(S14-2);(A2-33)+(S14-3);(A2-34)+(S1-1);
(A2-34)+(S1-7);(A2-34)+(S1-11);(A2-34)+(S2-1);(A2-34)+(S3-1);
(A2-34)+(S3-2);(A2-34)+(S3-4);(A2-34)+(S3-7);(A2-34)+(S3-8);
(A2-34)+(S3-10);(A2-34)+(S3-11);(A2-34)+(S4-1);(A2-34)+(S4-5);
(A2-34)+(S4-6);(A2-34)+(S11-1);(A2-34)+(S11-2);(A2-34)+(S11-3);
(A2-34)+(S13-1);(A2-34)+(S13-2);(A2-34)+(S13-3);(A2-34)+(S13-8);
(A2-34)+(S14-1);(A2-34)+(S14-2);(A2-34)+(S14-3);(A2-35)+(S1-1);
(A2-35)+(S1-7);(A2-35)+(S1-11);(A2-35)+(S2-1);(A2-35)+(S3-1);
(A2-35)+(S3-2);(A2-35)+(S3-4);(A2-35)+(S3-7);(A2-35)+(S3-8);
(A2-35)+(S3-10);(A2-35)+(S3-11);(A2-35)+(S4-1);(A2-35)+(S4-5);
(A2-35)+(S4-6);(A2-35)+(S11-1);(A2-35)+(S11-2);(A2-35)+(S11-3);
(A2-35)+(S13-1);(A2-35)+(S13-2);(A2-35)+(S13-3);(A2-35)+(S13-8);
(A2-35)+(S14-1);(A2-35)+(S14-2);(A2-35)+(S14-3);(A2-36)+(S1-1);
(A2-36)+(S1-7);(A2-36)+(S1-11);(A2-36)+(S2-1);(A2-36)+(S3-1);
(A2-36)+(S3-2);(A2-36)+(S3-4);(A2-36)+(S3-7);(A2-36)+(S3-8);
(A2-36)+(S3-10);(A2-36)+(S3-11);(A2-36)+(S4-1);(A2-36)+(S4-5);
(A2-36)+(S4-6);(A2-36)+(S11-1);(A2-36)+(S11-2);(A2-36)+(S11-3);
(A2-36)+(S13-1);(A2-36)+(S13-2);(A2-36)+(S13-3);(A2-36)+(S13-8);
(A2-36)+(S14-1);(A2-36)+(S14-2);(A2-36)+(S14-3);
In the context of the present invention, especially the compound of preferred formula (I) and the combination of following safener: mefenpyrdiethyl, fenchlorazole, the acid of Shuan Ben oxazole, cloquitocet_mexyl, allyl dichloride amine (dichlormid), 3-dichloro-acetyl-2, 2, 5-trimethylammonium-1, the 3-oxazolidine, benoxacor, 3-dichloro-acetyl-1-oxa--3-azaspiro [4, 5] decane, 1-dichloro-acetyl azepan, Xie Cao oxazole (furilazole), ((R)-3-dichloro-acetyl-5-(2-furyl)-2, 2-bis-Jia Ji oxazolidine), cyclopropyl-sulfonylamide (cyprosulfamide), N-sec.-propyl-4-sulfamyl benzamide, 1-(2-p-methoxy-phenyl) ethyl ketone, 1-[4-(N-2-anisoyl sulfamyl) phenyl]-the 3-MU, oxabetrinil, fluxofenim, cyometrinil, 1, 8-naphthalene dicarboxylic acids acid anhydride, fenclorim (fenclorim), separate careless amine, O-phenyl thiophosphoric acid O, O--diethyl ester (dietholate), dimepiperate, daimuron and cumyluron.
In the context of the present invention, the extremely particularly preferably compound of general formula (I) and the combination of following safener: daimuron, benoxacor, Xie Cao oxazole, fluxofenim, fenchlorazole (ethyl ester), mefenpyrdiethyl, cloquitocet_mexyl, the acid of Shuan Ben oxazole, cyclopropyl-sulfonylamide, solution grass amine, oxabetrinil, allyl dichloride amine, O-phenyl thiophosphoric acid O, O--diethyl ester.
Lower of the present invention, the even more preferably compound of general formula (I) and the combination of following safener: mefenpyrdiethyl, two benzene oxazole acid, cyclopropyl-sulfonylamide, fenchlorazole ethyl ester, benoxacor, cloquitocet_mexyl, fluxofenim are conciliate careless oxazole.
The compound or its salt and (B) herbicide-safener combination of one or more safeners of detoxicating activity amount that preferably comprise one or more formulas (I) of (A) weeding activity amount.
" weeding activity amount " means to be applicable to adversely to affect the amount of one or more weedicides of plant-growth in the context of the invention." detoxicating activity amount " means to be applicable to reduce the amount of activeconstituents in crop production compositions (for example weedicide) to one or more safeners of the phytotoxic effects of crop plants in the context of the present invention.
The weedicide that safener (B) is applicable to be reduced in general formula (I) issuable phytotoxic effects during for the useful plant crop, and can not weaken significantly the effect of these active herbicidal constituents opposing noxious plants.Just because of this, can expand significantly the Application Areas of conventional crop production compositions, for example the crop for not using so far weedicide fully or can only limited extent ground use weedicide.
According to indication and active herbicidal constituents used, the rate of application of required safener can change in wide region, is generally per hectare 0.001 to 5kg, and preferably 0.005 to 2.5kg and the activeconstituents that is in particular 0.05 to 0.5kg.
The active herbicidal constituents (A) of general formula (I) and safener (B) can for example pass through spraying, pouring and spray, or use together (for example conduct is with preparation or by the mixed method of bucket) by broadcasting sowing particle or in succession use with any order.The weedicide (A) of general formula (I): the weight ratio of safener (B) can change in wide region, and preferably from 1:10000 to 10000:1, especially from 1:1000 to 1000:1 and extremely especially from 1:20 to 20:1 general formula (I) (A) and safener (B) optimum amount in each case depend on the type of weedicide used and safener used, and character and the etap of depending on pending plant material, and can determine by simple conventional pilot study in all cases.
According to their character, the safener existed in herbicide-safener combination of the present invention (B) can be used for the seed (for example, for seed dressing) of pre-treatment crop plants or introduces prior to seeding furrow, or together with weedicide, is using before plant emerges or after emerging.The pre-treatment of emerging not only is included in sowing pre-treatment cultural area (comprising any water existed on cultural area, for example, for being applied to rice), and comprises that processing sowed seed but not yet covered the cultural area of growing plant.Preferably together with described weedicide, use.For this purpose, can use the mixed thing of bucket or use preparation.
In a preferred embodiment,---optionally with other active agrochemistry compositions, be combined---with described safener (B) seed (for example grain, seed or for example germination position of stem tuber or bud of organ of nourishing and generating) or seedling are carried out to pre-treatment.Pre-treatment for seed, described activeconstituents for example can be applied to seed by seed dressing, maybe described activeconstituents and described seed can be joined in water or other solvents, and described activeconstituents can be for example by the absorption in steeping process or diffusion or absorb by swelling or vernalization.For the processing of seedling, for example can be by spraying, dipping or pouring---optionally be combined other active agrochemistry compositions---contact transplanting subsequently and optionally use weedicide (A) to carry out aftertreatment by shoot and described safener.
Seed or seedling can be processed with safener (B) individually or for example, be processed with safener (B) and other active agrochemistry compositions (mycocide, insecticide or plant reinforcer, fertilizer or swelling and the promotor of emerging) combination.After pre-treatment is used, subsequently can be by described safener the weedicide at one or more formulas (I)---also can in conjunction with other known weedicides---before, again use afterwards or together.Pre-treatment to seed or seedling can realize the raising to the safener long-acting.
Therefore, it is a kind of for preventing and treating the method for the undesired plant of plant crop that the present invention also provides, it is characterized in that by the component of herbicide-safener combination of the present invention (A) and (B) for example being applied to respectively or jointly described plant (noxious plant for example, as monocotyledon weed or broadleaf weed or undesired crop plants), seed (for example grain, seed or the organ of nourishing and generating, as the germination position of stem tuber or bud) or plant-growth zone (for example cultural area).Here, can be by one or more especially a kind of compounds of one or more safeners (B), preferred group (S1) to (S15) at the weedicide (A) of general formula (I) before, be applied to described plant, seed or plant-growth zone (for example cultural area) afterwards or with it simultaneously.In a preferred embodiment, described safener (B) is for the treatment of seed.
Undesired plant is understood to imply all plants that give birth in the place not wanting their growths.For example, these can be noxious plant (for example unifacial leaf or broadleaf weed or undesired crop plants), for example comprise that for example glyphosate, atrazine, Glufosinate or imidazolidinone weedicide have those of resistance to some active herbicidal constituents.
Monocotyledon weed is for example carried out to the classification with the subordinate, Echinochloa (Echinochloa), setaria (Setaria), Panicum (Panicum), knotgrass (Digitaria), ladder forage spp (Phleum), Poa L. (P0a), festuca (Festuca), yard grass belongs to (Eleusine), Brachiaria (Brachiaria), lolium (Lolium), Brome (Bromus), Avena (Avena), Cyperus (Cyperus), sorghum (Sorghum), Agropyron (Agropyron), Cynodon (Cynodon), Monochoria (Monochoria), genus fimbristylis (Fimbristylis), Sagittaria (Sagittaria), Eleocharis (Eleocharis), Scirpus (Scirpus), Paspalum (Paspalum), ischaemum (Ischaemum), cusp Pittosporum (Sphenociea), talon eria (Dactyloctenium), Agrostis (Agrostis), amur foxtail belongs to (Alopecurus), Apera belongs to.Broadleaf weed is for example carried out to the classification with the subordinate, and sinapsis alba belongs to (Sinapis), separate row Vegetable spp (Lepidium), galium (Galium), Stellaria (Stellaria), Matricaria (Matricaria), Anthemis (Anthemis), ox achyranthes chrysanthemum spp (Galinsoga), Chenopodium (Chenopodium), Urtica (Urtica), Senecio (Senecio), Amaranthus (Amaranthus), Portulaca (Portulaca), Xanthium (Xanthium), japanese bearbind belongs to (Convolvulus), Ipomoea (Ipomoea), Polygonum (Polygonum), Daubentonia (Sesbania), Ambrosia (Ambrosia), Cirsium (Cirsium), bristlethistle (Carduus), sonchus L (Sonchus), Solanum (Solanum), Han Lepidium (Rorippa), joint joint Lepidium (R0tala), Vandellia (Lindernia), lamium (Lamium), Veronica (Veronica), abutilon (Abutilon), thorn Rumex (Emex), Datura (Datura), Viola (Viola), the weasel hemp nettle belongs to (Galeopsis), papaver (Papaver), bachelor's-button (Centaurea), Clover (Trifolium), Ranunculus (Ranunculus), Dandelion (Taraxacum), Euphorbia (Euphorbia).
Preferably, in the method for the invention, use the component (A) of significant quantity and (B) with the noxious plant in control plant crop, described plant crop is important farm crop economically for example, unifacial leaf farm crop for example, for example, as cereal (wheat, barley, rye, oat), rice, corn, broomcorn millet/Chinese sorghum; Or dicotyledonous farm crop, for example sugar beet, rape, cotton, Sunflower Receptacle and leguminous plants for example, for example, as Glycine (soybean, for example, as non-transgenic soybean (conventional variety is as the STS kind)) or genetically engineered soybean (RR soybean or LL soybean) and cross-fertilize seed thereof), Phaseolus, Pisum, Vicia and Arachis; Or the vegetable crop of different plants genus, for example potato, leek, wild cabbage, Radix Dauci Sativae, tomato, onion; And permanent crop and plantation crops, for example a kind of fruit, such as apple, pear, etc. and drupe, berry, grape, hevea, banana, sugarcane, coffee, tea, oranges and tangerines, nut planting plants, lawn, palm crops and forestry crop.
The present invention also provides herbicide-safener combination of the present invention for preferably the plant crop, preventing and treating the purposes of undesired plant.
Can prepare by currently known methods by herbicide-safener combination of the present invention, for example with each component optionally with the mixed preparation of other activeconstituentss, additive and/or conventional formulation auxiliary agent, then it is used after dilute with water in a usual manner, or by the mixed thing of so-called bucket that preparation or each component of partly preparing respectively and water dilute altogether respectively.Can also use at different time each component that (separate administration) prepared respectively or part is prepared respectively.Also can for example with many parts, use each component or herbicide-safener combination (sequential application), for example before emerging, use, then use after being emerged, or use after emerging in early days, then carry out mid-term or later stage and use after emerging.Preferably jointly use or the described binding substances of sequential application in activeconstituents.
Herbicide-safener combination of the present invention also is used in crop known or still undeveloped genetically modified plant and prevents and treats noxious plant.
Usually, transgenic plant be take particularly advantageous character as feature, for example, to some agricultural chemicals resistance of---particularly some weedicide---, for example, to Plant diseases or cause the resistance of Plant diseases organism (some insect or microorganism are as fungi, bacterium or virus).Other concrete properties relate to, for example, and the quantity of harvested material, quality, storage, composition and concrete composition.For example, there are the transgenic plant that different lipid acid forms in the transgenic plant of the starch quality of the known starch content with raising or change or harvested material.Other concrete properties can be for to abiotic stress factor for example tolerance or the resistance of hot, cold, arid, salt and ultraviolet radiation.
Preferably in the genetically modified crops with Important Economic value of useful plant and ornamental plant, use herbicide-safener combination of the present invention or its salt, described crop is cereal (as wheat, barley, rye, oat), broomcorn millet/Chinese sorghum, rice, cassava and corn for example, or the crop of beet, cotton, rape, potato, tomato, pea and other vegetables.
The compound of formula (I) can be preferably be used as weedicide in the plant poison effect to weedicide has resistance or by recombination method, produces the crop of useful plant of resistance.
Preparation is compared the ordinary method with the new plant that improves characteristic and is comprised for example conventional breeding method and mutant generation method with existing plant.Perhaps, there is the new plant that improves characteristic and can produce by recombination method (referring to for example, EP-A-0221044, EP-A-0131624) preparation.For example, following situation has been described in a plurality of cases:
-crop plants is for example carried out to genetic modification, with starch synthetic in improved plant (WO92/11376, WO92/14827, WO91/19806),
-genetically modified crops plant that some Glufosinate class weedicide (referring to for example EP-A-0242236, EP-A-242246) or glyphosate (gluphosate) class weedicide (WO92/00377) or sulfonylurea herbicide (EP-A-0257993, US-A-5013659) are had to resistance
-can produce thuringiensis bacillus toxin (Bt toxin) thus make plant there is the genetically modified crops plant of resistance to some insect, cotton (EP-A-0142924, EP-A-0193259) for example,
-there is the genetically modified crops plant (WO91/13972) that the lipid acid of change forms,
-thering is the genetic modification crop plants of new constituent or secondary metabolite, described new constituent or secondary metabolite are for example to produce the novel plant toxinicide (phytoalexins) (EPA309862, EPA0464461) of the disease resistance strengthened,
-thering is the genetically modified plant of the photorespiration of minimizing, it has high yield and higher stress tolerance (EPA0305398),
The genetically modified crops plant (" molecule farm (molecular pharming) ") of the key protein of-generation pharmacy or diagnosis aspect.
-take the genetically modified crops plant that higher output yield or better quality be feature,
-genetically modified crops plant that for example combination of above-mentioned new capability (" gene stacking ") of take is feature.
Many molecular biotechnologies that can be used for preparing the new transgenic plant with improvement character are known in principle, referring to for example L Potrykus and G.Spangenberg (volume) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, " Trends in Plant Science " 1 (1996) 423-431
In order to carry out this class reorganization operation, can will can produce sudden change or produce by recombinant DNA sequence the nucleic acid molecule introducing plasmid that sequence changes.By means of standard method, can for example carry out the base replacement, can remove partial sequence or add natural or synthetic sequence.For DNA fragmentation is connected to each other, can add linker (adapter) or connector (1inker) to fragment.For example referring to, the people such as Sambrook, 1989, Molecular Cloning, A Laboratory Manual, second edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; Or Winnacker " Gene und Klone ", VCH Weinheim second edition, 1996.
For example, the generation of vegetable cell with gene product of activity decreased can realize by following method: by expressing at least one corresponding sense-rna or for realizing the just RNA of co-suppression effect, or by the transcript of expressing at least one specificity cutting said gene product the ribozyme with suitable construction.
For this purpose, can at first use the whole encoding sequences that the comprise gene product DNA molecular of---comprising any flanking sequence that may exist---, or only comprising the DNA molecular of part encoding sequence, wherein said part encoding sequence must sufficiently long, in order to produce the antisense effect in cell.Also can use with the encoding sequence of described gene product and there is high homology but not identical DNA sequence dna.
When express nucleic acid in plant divides the period of the day from 11 p.m. to 1 a.m, the albumen of synthesized can be positioned in any required compartment of vegetable cell.Yet, in order to realize the location in specific compartment, can for example coding region be connected with guarantee the DNA sequence dna of locating in specific compartment.This sequence is that known (referring to such as people such as Braun, EMBO is (1992) J.11,3219-3227 for those skilled in the art; The people such as Wolter, Proc.Natl.Acad.Sci.USA85 (1988), 846-850; The people such as Sonnewald, Plant is (1991) J.1,95-106).Nucleic acid molecule also can be expressed in the organoid in vegetable cell.
Can be by known technology regeneration of transgenic vegetable cell to produce complete plant.In principle, described transgenic plant can be the plant of any required plant variety, both can be monocotyledons, also can be dicotyledons.
Therefore, can express, check or suppress by the mistake to homology (natural) gene or gene order, or obtain by the expression of allos (being external source) gene or gene order the transgenic plant that character changes.
Preferably; herbicide-safener combination of the present invention can be used in genetically modified crops; described genetically modified crops to growth regulator for example dicamba 98 there is resistance; perhaps to suppressing the weedicide of important plant enzyme; for example acetolactate synthestase (ALS), epsp synthase, glutamine synthetase (GS) or hydroxyphenylphruvic acid dioxygenase (HPPD) have resistance, or the weedicide that is selected from sulfonylurea, glyphosate, Glufosinate or benzoyl isoxzzole and similar activeconstituents is had to resistance.
When herbicide-safener combination of the present invention is used for to genetically modified crops, except the effect for noxious plant that can observe in other crops, also often find to be applied to the special effect of specific genetically modified crops, for example change or operable rate of application when the weeds that can the prevent and treat spectrum of special broadening, improved using, with described genetically modified crops, it had to the more excellent compatibility of the weedicide of resistance, and on the growth of genetically modified crops plant and the impact of output.
Therefore, the present invention also provides the purposes of the noxious plant of herbicide-safener combination of the present invention for preventing and treating the genetically modified crops plant.
Preferably useful plant and ornamental plant have that Important Economic is worth genetically modified crops in use binding substances of the present invention or its salt, described crop example cereal (as wheat, barley, rye, oat), broomcorn millet/Chinese sorghum, rice, cassava and corn, or the crop of sugar beet, cotton, soybean, rape, potato, tomato, pea and other vegetables.
Therefore, the present invention also provides herbicide-safener combination of the present invention for the genetically modified crops plant or have the purposes of the crop plants control noxious plant of tolerance by selection breeding.
Described weedicide (A) and described safener (B) can be together or are converted to respectively conventional formulation, for example for by spraying, pouring, spray and the using of seed dressing, described conventional formulation is solution, emulsion, suspension agent, pulvis, foaming agent, paste, granule, aerosol, the natural and synthetic through the activeconstituents dipping, the microcapsule in polymeric material for example.Described preparation can comprise conventional auxiliary agent and additive.
These preparations can be produced by known methods, for example, by described activeconstituents is mixed with weighting agent (being liquid solvent, pressurized liquefied gas and/or solid carrier), optionally use tensio-active agent (being emulsifying agent and/or dispersion agent and/or whipping agent).
If weighting agent used is water, for example also may use organic solvent as secondary solvent.Useful liquid solvent mainly contains: aromatic substance, for example dimethylbenzene, toluene, alkylnaphthalene; Chloro aromatic substance or chloro aliphatic hydrocrbon, for example chlorobenzene, vinylchlorid or methylene dichloride; Aliphatic hydrocrbon, for example hexanaphthene or paraffin, as mineral oil fraction, mineral oil and vegetables oil; Alcohols, for example butanols or glycol, and their ether and ester; Ketone, for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Intensive polar solvent, for example dimethyl formamide or dimethyl sulfoxide (DMSO); And water.
Useful solid carrier comprises: for example natural mineral of ammonium salt and pulverizing (for example kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite) and the synthetic materials (for example finely divided silicon-dioxide, aluminum oxide and silicate) pulverized; Useful solid carrier for granule is: for example, the also natural rock (for example calcite, marble, float stone, sepiolite and rhombspar) of classification of pulverizing, and synthetic inorganic and organic powder particles, and the particle of organic materials (for example sawdust, Exocarpium cocois (Cocos nucifera L), corn cob and tobacco stem); Useful emulsifying agent and/or whipping agent comprise: for example nonionic and anionic emulsifier are (as polyoxyethylene fatty acid ether, polyoxyethylene aliphatic alcohol ether, for example alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate), and protein hydrolyzate; Useful dispersion agent comprises: for example lignin sulfite waste lye and methylcellulose gum.
Can use tackifier in described preparation; the for example natural and synthetic polymer of carboxymethyl cellulose and powder, particle or latex form (for example gum arabic, polyvinyl alcohol and polyvinyl acetate), and natural phospholipid (for example kephalin and Yelkin TTS) and synthetic phospholipid.Other additives can be mineral oil and vegetables oil.
Can use dyestuff, for example mineral dye (for example ferric oxide, titanium oxide and Prussian blue) and organic dye (for example alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff), and micro-nutrients, for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Described preparation generally includes the activeconstituents of 0.1-95 % by weight, preferred 0.5-90 % by weight.
Described weedicide (A) and described safener (B) can itself form or with itself and the use of the dosage form mixed of other agricultural chemical activity compositions (example is weedicide as is known), for preventing and treating undesired plant, for example, for controlling weeds or for preventing and treating undesired crop, described formulation example is as can be for preparation or the mixed thing of bucket.
Activeconstituents that also can be known with other mixes mutually; for example mycocide, insecticide, miticide, nematocides, bird repellent, plant nutrient agent and Soil structure improving agent, can also be usually used in plant protection in additive and formulation auxiliary agents mix mutually.
Described weedicide (A) and described safener (B) can itself form be used, and use or use with the type of service by further dilution preparation with its dosage form, for example ready to use solution, suspension, emulsion, powder, paste and granule.Usually for example by watering, spray, spray or broadcasting sowing and used.
Described activeconstituents can be applied to plant, plant parts, seed or cultural area (farmland), preferably be applied to seed or green plants and plant parts, and optionally also be applied to farmland.A kind of method of application is that described activeconstituents is co-administered with the mixed thing form of bucket, now the concentrate formulation through the optimization preparation of single activeconstituents is mixed with water in bucket, and uses obtained spraying fluid.
The advantage of the combined preparation of activeconstituents of the present invention (A) and binding substances (B) is that it is easy to use, because the amount of described component is with optimum proportion setting each other.In addition, the auxiliary agent optimization adjustment each other in described preparation.
Can take mixed preparation or the material that is combined with of the mixed form of bucket with herbicide-safener combination of the present invention as the example activeconstituents based on following enzyme is suppressed (preferably weeding) as is known: acetolactate synthase, acetyl-CoA carboxylase, PS I, PS II, HPPDO, phytoene desaturase, proporphyrinogen oxidase, glutamine synthetase, cellulose biosynthesis enzyme, 5-enol pyruvylshikimate-3-phosphate synthase.Described compound and other available compounds---some mechanism of action are unknown or different---be recorded in following document for example and the document wherein quoted in: Weed Research26,441-445 (1986), or handbook " The Pesticide Manual ", 2000 the 12nd editions, or 2003 the 13rd editions or 2006/2007 the 14th edition, or corresponding " e-Pesticide Manual " the 5.0th edition (2008-10), abovely by British Crop Protection Council (hereafter is " PM "), publish.Also can find the popular name list in " sterilant popular name outline (Thecompendium of Pesticide Common Names) " on the internet.(annotate: " popular name " or chemical name that described compound can International Standards Organization (ISO) regulation mean the following active ingredients that can comprise in conjunction with the weedicide example of herbicide-safener combination of the present invention of knowing from described document, in some cases also with standard number, and described compound always comprises all types of service, for example acid, salt, ester and isomer, for example steric isomer and optically active isomer.Mention a kind of application form herein, and mention in some cases multiple application form):
2,4-D, Acetochlor (acetochlor), acifluorfen (acifluorfen, acifluorfen-sodium), aclonifen (aclonifen), alachlor (alachlor), alloxydimsodium (alloxydim, alloxydim-sodium), ametryn (ametryn), amicarbazone (amicarbazone), amidosulfuron (amidosulfuron), chlorine Fampridine acid (aminopyralid), Amrol (amitrole), anilofos (anilofos), sulphur grass spirit (asulam), atrazine (atrazine), azafenidin (azafenidin), azimsulfuron (azimsulfuron), beflubutamid (beflubutamid), benazolin (benazolin, benazolin-ethyl), benfuresate (benfuresate), bensulfuron-methyl (bensulfuron-methyl), bentazone (bentazone), benzfendizone (benzfendizone), benzobicylon (benzobicyclon), benzofenap (benzofenap), bifenox (bifenox), bialaphos (bilanafos), two careless ethers (bispyribac-sodinm), bromacil (bromacil), bromobutide (bromobutide), bromofenoxim (bromofenoxim), Brominal (bromoxynil), butachlor (butachlor), butafenacil (butafenacil), butenachlor (butenachlor), butralin (butralin), fourth oxygen cyclic ketones (butroxydim), butylate (butylate), cafenstrole (cafenstrole), carbetamide (carbetamide), carfentrazoneethyl (carfentrazone-ethyl), chlomethoxyfen (chlomethoxyfen), chloridazon (chloridazon), chlorimuronethyl (chlorimuron-ethyl), Mo 9 granular (chlornitrofen), chlortoluron (chlortoluron), chlorine sulphur grand (chlorsulfuron), cinidon-ethyl (cinidon-ethyl), cinmethylin (cinmethylin), cinosulfuron (cinosulfuron), clefoxidim (clefoxydim), clethodim (clethodim), clodinafop-propargyl (clodinafop-propargyl), clomazone (clomazone), clomeprop (clomeprop), clopyralid (clopyralid), cloransulammethyl (cloransulam-methyl), cumyluron (cumyluron), cyanazine (cyanazine), AC322140 (cyclosulfamuron), cycloxydim (cycloxydim), cyhalofop-butyl (cyhalofop-butyl), desmedipham (desmedipham), Mediben (dicamba), dichlobenil (dichlobenil), 2,4-drips propionic acid (dichlorprop), essence 2,4-drips propionic acid (dichlorprop-P), diclofop-methyl (diclofop-methyl), diclosulam (diclosulam), difenzoquat (difenzoquat), diflufenican (diflufenican), difluoro pyrrole grand (diflufenzopyr), dikegulac (dikegulac-sodium), dimefuron (dimefuron), dimepiperate (dimepiperate), dimethachlor (dimethachlor), dimethametryn (dimethametryn), dimethenamid (dimethenamid), triaziflam (triaziflam), diquat dibromide (diquat-dibromide), dithiopyr (dithiopyr), diuron (diuron), Sha flutters grand (dymron), EPTC, esprocarb (esprocarb), ethalfluralin (ethalfluralin), ethametsulfuron (ethametsulfuron-methyl), ethofumesate (ethofumesate), HC252 (ethoxyfen), ethoxysulfuron (ethoxysulfuron), ethobenzanid (etobenzanid), oxazole diclofop-methyl (fenoxaprop-ethyl), fenoxaprop (fenoxaprop-P-ethyl), fentrazamide (fentrazamide), flampropisopropyl (flamprop-M-isopropyl), flampropmethyl (flamprop-M-methyl), flazasulfuron (flazasulfuron), florasulam (florasulam), fluazifop (fluazifop), fluazifop butyl ester (fluazifop-butyl), efficient fluazifop butyl ester (fluazifop-P-butyl), fluazolate (fluazolate), flucarbazonesodium (flucarbazone-sodium), flucetosulfuron (flucetosulfuon), fluchloraline (fluchloralin), flufenacet (flufenacet), flufenpyr, Flumetsulam (flumetsulam), Flumiclorac pentyl (flumiclorac-pentyl), flumioxazin (flumioxazin), fluometuron (fluometuron), fluorochloridone (fluorochloridone), fluoroglycofen-ethyl (fluoroglycofen-ethyl), flupoxam (flupoxam), flupyrsulfuron-methyl-sodium, fluridone (fluridone), fluroxypyr (fluroxypyr, fluroxypyr-butoxypropyl), meptyl ester (fluroxypyr-meptyl), flurprimidol (flurprimid0l), flurtamone (flurtamone), fluthiacetmethyl (fluthiacet-methyl), fomesafen (fomesafen), formyl ammonia sulphur grand (foramsulfuron), grass ammonium phosphine (glufosinate, glufosinate-ammonium), essence careless ammonium phosphine (glufosinate-P, glufosinate-P-ammonium), the careless ammonium phosphine of essence (sodium) (glufosinate-P-sodium), glyphosate (glyphosate), halosulfuronmethyl (halosulfuron-methyl), fluazifop-butyl (haloxyfop), fluazifop-butyl ethoxy ethyl ester (haloxyfop-ethoxyethyl), fluazifop-butyl methyl esters (haloxyfop-methyl), smart fluazifop-butyl methyl esters (haloxyfop-P-methyl), hexazinone (hexazinone), miaow oxalic acid (imazamethabenz-methyl), imazamox (imazamox), AC 263222 (imazapic), imazapyr (imazapyr), imazaquin (imazaquin), imazethapyr (imazethapyr), imazosulfuron (imazosulfuron), indanofan (indanofan), triazine indenes grass amine (indaziflam), iodosulfuron methyl sodium (iodosulfuron-methyl-sodium), ioxynil (ioxynil), isoproturon (isoproturon), isouron (isouron), ixoxaben (isoxaben), isoxachlorotole (isoxachlortole), isoxazole humulone (isoxaflutole), ketospiradox, lactofen (lactofen), lenacil (lenacil), linuron (linuron), MCPA, Vi par (mecoprop), mecopropP (mecoprop-P), mefenacet (mefenacet), first sulfanilamide (SN) semi-annular jade pendant grand (mesosulfuron-methyl), mesotrione (mesotrione), oxazole acyl grass amine (metamifop), metamitron (metamitron), metazachlor (metazachlor), methabenzthiazuron (methabenzthiazuron), methiozolin, methyldymron (methyldymron), metobromuron (metobromuron), isopropyl methoxalamine (metolachlor), metosulam (metosulam), metoxuron (metoxuron), piperazine humulone (metribuzin), metsulfuron-methyl (metsulfuron-methyl), molinate (molinate), afesin (monolinuron), naproanilide (naproanilide), napropamide (napropamide), neburea (neburon), nicosulfuron (nicosulfuron), norflurazon (norflurazon), orbencarb (orbencarb), oryzalin (oryzalin), oxadiargyl (oxadiargyl), oxadiazon (oxadiazon), oxasulfuron (oxasulfuron), oxaziclomefone (oxaziclomefone), Oxyfluorfen (oxyfluorfen), paraquat (paraquat), n-nonanoic acid (pelargonic acid), pendimethalin (pendimethalin), pendralin, penoxsuam (penoxsulam), pentoxazone (pentoxazone), pethoxamid (pethoxamid), phenmedipham (phenmedipham), picloram (picloram), fluorine pyrrole acyl grass amine (picolinafen), azoles quinoline grass ester (pinoxaden), piperophos (piperophos), the third careless amine (pretilachlor), primisulfuronmethyl (primisulfuron-methyl), profluazol (profluazol), clefoxidim (profoxydim), prometryn (prometryn), propachlor (propachlor), Stam F-34 (propanil), propaquizafop (propaquizafop), propisochlor (propisochlor), procarbazone (propoxycarbazone-sodium), propyrisulfuron, propyzamide (propyzamide), prosulfocarb (prosulfocarb), prosulfuron (prosulfuron), pyraclonil (pyraclonil), pyrrole grass ether (pyraflufen-ethyl), pyrazolate (pyrazolate), pyrazosulfuron (pyrazosulfuron-ethyl), pyrazoxyfen (pyrazoxyfen), pyribenzoxim (pyribenzoxim), pyributicarb (pyributicarb), pyridafol, pyridate (pyridate), pyriftalid (pyriftalide), KIH 6127 (pyriminobac-methyl), pyrithiobac-sodium (pyrithiobac-sodium), dichloro quinolinic acid (quinclorac), quinmerac (quinmerac), quinoclamine (quinoclamine), quizalofop-ethyl ethyl ester (quizalofop-ethyl), Quizalotop-ethyl ethyl ester (quizalofop-P-ethyl), quizalofopPtefuryl (quizalofop-P-tefuryl), rimsulfuron (rimsulfuron), sethoxydim (sethoxydim), Simanex (simazine), symetryne (simetryn), isopropyl methoxalamine (S-metolachlor), sulphur humulone (sulcotrione), sulfentrazone (sulfentrazone), sulfometuronmethyl (sulfometuron-methyl), sulphosate (sulfosate), Sulfosulfuron (sulfosulfuron), tebuthiuron (tebuthiuron), tepraloxydim (tepraloxydim), Garagard (terbuthylazine), terbutryn (terbutryn), P DimethenamidP (thenylchlor), azoles nicotinic acid (thiazopyr), thifensulfuronmethyl (thifensulfuron-methyl), benthiocarb (thiobencarb), tiocarbazil (tiocarbazil), tralkoxydim (tralkoxydim), triallate (triallate), triasulfuron (triasulfuron), tribenuron-methyl (tribenuron-methyl), trichlopyr (triclopyr), tridiphane (tridiphane), trifloxysulfuron (trifloxysulfuron), trefanocide (trifluralin), triflusulfuronmethyl (triflusulfuron-methyl) and tritosulfuron (tritosulfuron).
Other possible mixing elements are
Pyroxasulfone, pyroxsulam (pyroxsulam), phonetic aniline sulphur grand (orthosulfamuron), Nylar (pyrimisulfan), adjust naphthenic acid (prohexadione-calcium), bencarbazone, SYN-523, IDH-100, SYP-249, monosulfmeturon (monosulfuron), ipfencarbazone (HOK-201), iso-propyl-ester nitrofen (pyribambenz-isopropyl), special furan triketone (tefuryltrione), bencarbazone, tembotrione, sulphonyl grass pyrazoles (pyrasulfotole) and thiophene ketone sulphur grand (thiencarbazone-methyl).
For using, if suitable, the preparation of commercial form is diluted in a usual manner, but for example in the situation that wettable powder emulsion concentrate, dispersion agent and water-dispersible granules make dilute with water.Before using, powder agent, soil are no longer further diluted with other inert substances usually with granule or for granule and the sprayable solution agent of broadcasting sowing.
Biological Examples:
Emerge rear herbicide effect and safener effect
The seed of unifacial leaf and dicotyledonous harmful plants and crop plants or rhizome partly are placed in to the peat basin that fills sandy loam, cover with soil, grow in greenhouse under better growing conditions.Perhaps, the noxious plant that occurs in Rice Cropping is planted in the moisture basin that is deep to 2cm above soil surface.After planting ten days to 20 days, processed the described test plant in one to tri-leaf period.Each activeconstituents that is mixed with the herbicide-safener combination of the present invention of water solube powder or suspension agent and corresponding preparation in parallel test is sprayed on the green plants position with various dose, the water rate of application is 300l/ha (scaled value), and test plant is kept standing 2-3 week in the greenhouse under optimal growth condition, compare the effect of visually rank preparation with untreated control group.Plant the noxious plant of middle appearance for rice or seed rice, also described activeconstituents directly can be added in irrigation water to (being similar to particle uses) or be sprayed in plant and irrigation water.
Described test shows with each weedicide that does not contain safener and compares, and herbicide-safener combination of the present invention reduces for example, infringement to crop plants (corn, rice, wheat, barley) significantly, and 30% to as high as 100%.Simultaneously, described weedicide does not affect at all or does not obviously weaken the effect of important economically noxious plant, and can realize resisting the like this good rear herbicide effect of emerging of broad-spectrum weeding and broadleaf weeds.
For example, in barley, for following herbicide-safener combination (A1-85)+(s1-1), (A1-85)+(S1-11), (A1-85)+(S4-1), (A1-85)+(S2-1), (A1-85)+(S3-4), (A1-85)+(S11-2), (A1-62)+(S1-1), (A1-62)+(S1-11), (A1-62)+(S4-1), (A1-62)+(S2-1), (A1-62)+(S3-4), (A1-62)+(S3-10) and (A1-62)+(S11-2), buy and showed the consistency good with crop plants and had the emerge rear herbicide effect good to the wide spectrum noxious plant simultaneously concurrently.
In wheat, for example, for following herbicide-safener combination (A1-85)+(S1-1), (A1-85)+(S1-11), (A1-85)+(S4-1), (A1-85)+(S2-1), (A1-85)+(S3-4), (A1-85)+(S3-10), (A1-85)+(S11-2), (A1-62)+(S1-11), (A1-62)+(S4-1), (A1-62)+(S2-1), (A1-62)+(S3-4), (A1-85)+(S3-10) with (A1-62)+(S11-2, buy and showed the consistency good with crop plants and had the emerge rear herbicide effect good to the wide spectrum noxious plant simultaneously concurrently.
In corn, for example, for following herbicide-safener combination (A1-85)+(s1-1), (A1-85)+(S1-11), (A1-85)+(S2-1) and (A1-85)+(S3-4), realized the consistency good with crop plants and had the emerge rear herbicide effect good to the wide spectrum noxious plant simultaneously concurrently.
Emerge front herbicide effect and safener effect
The seed of unifacial leaf and broadleaf weed plant and crop plants or rhizome partly are placed in to the peat basin that fills sandy loam, and cover with soil.Each activeconstituents that will be mixed with subsequently the herbicide-safener combination of the present invention of water solube powder or suspension agent and corresponding preparation in parallel test is applied to various dose on the surface of mulching soil, and the water rate of application is 600 to 800l/ha (scaled values).After processing, described basin is placed in to greenhouse, and remains under the excellent growing conditions that is suitable for weeds and crop plants.After the test duration of 2 to 4 weeks, with untreated control group, to compare, plant or the emerge infringement of described test plant after emerging recorded in range estimation,
In corn, for example, for following weedicide one safener combination, (A1-85)+(s1-11), (A1-85)+(S4-1), (A1-85)+(S2-1), (A1-85)+(S3-4), (A1-85)+(S3-10), (A1-85)+(S11-2), (A1-85)+(S1-7), (A1-62)+(S1-1), (A1-62)+(S4-1), (A1-62)+(S2-1), (A1-62)+(S3-4), (A1-85)+(S3-10), (A1-62)+(S11-2) and (A1-62)+(s1-7), realize the consistency good with crop plants and had the emerge front herbicide effect good to the wide spectrum noxious plant simultaneously concurrently.
Seed treatment
The kind grain of crop plants is mixed with the safener that is mixed with suspension agent or emulsion enriching agent and water in bottle and fully vibration, so that described kind grain is coated with various safener preparations equably.Subsequently the kind grain after emerging or plant are processed with weedicide by emerge front method or the rear method of emerging.A large amount of herbicide-safener combinations of the present invention show the consistency good with crop plants and have the herbicide effect good to the wide spectrum noxious plant simultaneously concurrently.

Claims (12)

1. one kind comprises following herbicide-safener combination
(A) compound or its salt of one or more formulas (I)
Figure FDA0000380526530000012
Wherein symbol and index are defined as follows separately:
W is N or CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, (C 2-C 6) thiazolinyl, (C 2-C 6) alkene oxygen base, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyl, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, methoxycarbonyl methyl, ethoxy carbonyl methyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl or be selected from separately heteroaryl, heterocyclic radical or the phenyl that s group of methyl, ethyl, methoxyl group, trifluoromethyl and halogen replaces
X and Z are nitro, halogen, cyano group, formyl radical, thiocyano, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 3-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, (C 3-C 6) halogenated cycloalkyl-(C 1-C 6) alkyl, COR 1, OR 1, OCOR 1, OSO 2R 2, S (O) nR 2, SO 2OR 1, SO 2N(R 1) 2, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-OCOR 1, (C 1-C 6) alkyl-OSO2R 2, (C 1-C 6) alkyl-COOR 1, (C 1-C 6) alkyl-SO 2OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, NR 1R 2, P (O) (OR 5) 2Or
Be selected from separately heteroaryl, heterocyclic radical or the phenyl of s group replacement of methyl, ethyl, methoxyl group, nitro, trifluoromethyl and halogen,
Y is hydrogen, nitro, halogen, cyano group, thiocyano, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 3-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, (C C-C 6) halogenated cycloalkyl-(C 1-C 6) alkyl, COR 1, CO 2R 1, OR 1, OCOR 1, OSO 2R 2, S (O) nR 2, SO 2OR 1, SO 2N(R 1) 2, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) miscellaneous alkyl aryl, O-(C 1-C 6) alkyl heterocyclic, O-(C 1-C 6) miscellaneous alkyl aryl, (C 1-C 6) alkyl heterocyclic, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-OCOR 1, (C 1-C 6) alkyl-OSO 2R 2, (C 1-C 6) alkyl-COOR 1, (C 1-C 6) alkyl-CN, (C 1-C 6) alkyl-SO 2OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, NR 1R 2, P (O) (OR 5) 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one, O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone, or
Be selected from separately heteroaryl or the heterocyclic radical of s group replacement of methyl, ethyl, methoxyl group, halogen and cyano methyl,
R 1For hydrogen, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) halogenated cycloalkyl, (C 1-C 6) alkyl-O-(C 1-C 6) alkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 12 groups are selected from cyano group, halogen, nitro, thiocyano, OR 3, S (O) nR 4, N(R 3) 2, NR 3OR 3, COR 3, OCOR 3, SCOR 3, NR 3COR 3, CO 2R 3, COSR 3, CON (R 3) 2(C 1-C 4) alkoxyl group-(C 2-C 6) s group of alkoxy carbonyl replace,
R 2For (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear seven groups are selected from cyano group, halogen, nitro, thiocyano, OR 3, S (O) nR 4, N (R 3) 2, NR 3OR 3, COR 3, OCOR 3, SCOR 3, NR 3COR 3, CO 2R 3, COSR 3, CON (R 3) 2(C 1-C 4) alkoxyl group-(C 2-C 6) s group of alkoxy carbonyl replace,
R 3For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl or (C 2-C 6) alkynyl,
R 4For (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl or (C 2-C 6) alkynyl,
R 5For methyl or ethyl,
N is 0,1 or 2,
S is 0,1,2 or 3,
And
(B) one or more safeners.
2. the herbicide-safener combination of claim 1, wherein
W is CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
Y is hydrogen, nitro, halogen, cyano group, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, OR 1, S (O) nR 2, SO 2OR 1, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one or O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
3. the herbicide-safener combination of claim 1, wherein
W is N,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
4. claim 1 or 2 herbicide-safener combination, wherein
W is CY,
R is hydrogen, (C 1-C 6) alkyl, (C 3-C 7) cycloalkyl, halo-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group, halo-(C 1-C 6) alkoxyl group, cyano group, nitro, methylthio group, methylsulfinyl, methyl sulphonyl, acetylamino, benzoyl-amido, methoxycarbonyl, ethoxy carbonyl, benzoyl, methyl carbonyl, piperidino carbonyl, trifluoromethyl carbonyl, halogen, amino, aminocarboxyl, methylamino carbonyl, dimethylamino carbonyl, methoxymethyl
X and Z are nitro, halogen, cyano group, (C independently of one another 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cycloalkyl, OR 1, S (O) nR 2, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2Or 1,2,4-triazol-1-yl,
Y is nitro, halogen, cyano group, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, OR 1, S (O) nR 2, SO 2OR 1, NR 1SO 2R 2, NR 1COR 1, (C 1-C 6) alkyl-S (O) nR 2, (C 1-C 6) alkyl-OR 1, (C 1-C 6) alkyl-CON (R 1) 2, (C 1-C 6) alkyl-SO 2N(R 1) 2, (C 1-C 6) alkyl-NR 1COR 1, (C 1-C 6) alkyl-NR 1SO 2R 2, tetrahydrofuran base oxygen ylmethyl, tetrahydrofuran base methoxymethyl, O (CH 2)-3,5-dimethyl-1,2-oxazole-4-base, O (CH 2) 2-O (3,5-dimethoxypyridin-2-base, O (CH 2)-5-pyrrolidin-2-one or O (CH 2)-5-2,4-dimethyl-2,4-dihydro-3H-1,2,4-triazole-3-ketone,
R 1For hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 3-C 6) cycloalkyl, (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, phenyl or phenyl-(C 1-C 6) alkyl, wherein rear 7 groups are selected from halogen and OR 3S group replace,
R 2For (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl or (C 3-C 6) cycloalkyl-(C 1-C 6) alkyl, wherein rear 3 groups are selected from halogen and OR 3S group replace,
R 3For hydrogen or (C 1-C 6) alkyl,
N is 0,1 or 2,
S is 0,1,2 or 3.
5. the described herbicide-safener combination of any one in claim 1,2 and 4, wherein
W is CY,
R is amino, cyclopropyl, sec.-propyl, n-propyl, methyl, ethyl, methoxyl group, bromine, chlorine or fluorine,
X is chlorine, trifluoromethyl or methyl,
Y is CH 2OCH 2CF 3, SO 2Me, S (O) Me or SMe,
Z is trifluoromethyl, SO 2Me, S (O) Me or SMe.
6. claim 1 or 3 herbicide-safener combination, wherein
W is CN,
R is amino, cyclopropyl, sec.-propyl, the tertiary butyl, methyl, ethyl, methoxyl group, bromine or chlorine,
X is chlorine, methoxymethyl or methyl,
Z is trifluoromethyl.
7. the herbicide-safener combination of any one in claim 1 to 6 comprises at least one and is selected from following safener:
Mefenpyrdiethyl, fenchlorazole, the acid of Shuan Ben oxazole, cloquitocet_mexyl, allyl dichloride amine, 3-dichloro-acetyl-2, 2, 5-trimethylammonium-1, the 3-oxazolidine, benoxacor, 3-dichloro-acetyl-1-oxa--3-azaspiro [4, 5] decane, 1-dichloro-acetyl azepan, Xie Cao oxazole, ((R)-3-dichloro-acetyl-5-(2-furyl)-2, 2-bis-Jia Ji oxazolidine), cyclopropyl-sulfonylamide, N-sec.-propyl-4-sulfamyl benzamide-1-(2-p-methoxy-phenyl) ethyl ketone, 1-[4-(N-2-anisoyl sulfamyl) phenyl]-the 3-MU, oxabetrinil, fluxofenim, cyometrinil, 1, 8-naphthalene dicarboxylic acids acid anhydride, fenclorim, separate careless amine, O-phenyl thiophosphoric acid O, the O-diethyl ester, dimepiperate, daimuron and cumyluron.
8. the herbicide-safener combination of claim 7 comprises at least one and is selected from following safener:
Daimuron, benoxacor, Xie Cao oxazole, fluxofenim, fenchlorazole (ethyl ester), mefenpyrdiethyl, cloquitocet_mexyl, the acid of Shuan Ben oxazole, cyclopropyl-sulfonylamide, solution grass amine, oxabetrinil, allyl dichloride amine, O-phenyl thiophosphoric acid O, the O-diethyl ester.
9. the herbicide-safener combination of claim 8, the compound that comprises general formula (I) at least and preferred following safener:
Mefenpyrdiethyl, the acid of Shuan Ben oxazole, cyclopropyl-sulfonylamide, fenchlorazole ethyl ester, benoxacor, cloquitocet_mexyl, fluxofenim are conciliate the Cao oxazole.
10. one kind for preventing and treating the method for crop noxious plant, it is characterized in that, one or more described composition in the claim 1 to 9 of weeding activity amount is applied to noxious plant, plant, plant seed or plant-growth zone.
11. the method for claim 10, is characterized in that, described plant is selected from sugarcane, corn, wheat, rye, barley, oat, rice, Chinese sorghum, cotton and soybean.
12. the method for claim 10 or 11, is characterized in that, described plant is genetic modification.
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